Jan Szargut - Exergy Method - Technical and Ecological Applications-WIT Press (UK) (2005)

Exergy Method
Technical and Ecological

Applications
WITPRESS
WIT Press publishes leading books in Science and Technology.
Visit our website for the current list of titles.
www.witpress.com
WITeLibrary
Home of the Transactions of the Wessex Institute, the WIT electronic-library provides the
international scientific community with immediate and permanent access to individual
papers presented at WIT conferences. Visit the WIT eLibrary at www.witpress.com.
International Series on Developments
in Heat T ransf
Transfer
ransfer
Objectives
The Developments in Heat Transfer book Series publishes state-of-the-art books and
provides valuable contributions to the literature in the field of heat transfer. The
overall aim of the Series is to bring to the attention of the international community
recent advances in heat transfer by authors in academic research and the engineering
industry.
Research and development in heat transfer is of significant importance to
many branches of technology, not least in energy technology. Developments include
new, efficient heat exchangers, novel heat transfer equipment as well as the introduction
of systems of heat exchangers in industrial processes. Application areas include heat
recovery in the chemical and process industries, and buildings and dwelling houses
where heat transfer plays a major role. Heat exchange combined with heat storage is
also a methodology for improving the energy efficiency in industry, while cooling in
gas turbine systems and combustion engines is another important area of heat
transfer research.
To progress developments within the field both basic and applied research
is needed. Advances in numerical solution methods of partial differential equations,
high-speed, efficient and cheap computers, advanced experimental methods using
LDV (laser-doppler-velocimetry), PIV (particle-image-velocimetry) and image
processing of thermal pictures of liquid crystals, have all led to dramatic advances
during recent years in the solution and investigation of complex problems within the
field.
The aims of the Series are achieved by contributions to the volumes from
invited authors only. This is backed by an internationally recognised Editorial Board
for the Series who represent much of the active research worldwide. Volumes planned
for the series include the following topics: Compact Heat Exchangers, Engineering
Heat Transfer Phenomena, Fins and Fin Systems, Condensation, Materials Processing,
Gas Turbine Cooling, Electronics Cooling, Combustion-Related Heat Transfer, Heat
Transfer in Gas-Solid Flows, Thermal Radiation, the Boundary Element Method in
Heat Transfer, Phase Change Problems, Heat Transfer in Micro-Devices, Plate-and-
Frame Heat Exchangers, Turbulent Convective Heat Transfer in Ducts, Enhancement
of Heat Transfer and other selected topics.
Series Editor
B. Sundén
Lund Institute of Technology
Box 118
22100 Lund
Sweden
Associate Editors
C.I. Adderley S. del Guidice

Rolls Royce and Associates Limited University of Udine
UK Italy
E. Blums M. Faghri
Latvian Academy of Sciences The University of Rhode Island
Latvia USA
C.A. Brebbia P.J. Heggs

Wessex Institute of Technology UMIST
UK UK
G. Comini C. Herman
University of Udine John Hopkins University
Italy USA
R.M. Cotta D.B. Ingham

COPPE/UFRJ, University of Leeds
Brazil UK
L. De Biase Y. Jaluria
University of Milan Rutgers University
Italy USA
G. De Mey S. Kotake
University of Ghent University of Tokyo
Belgium Japan
G. de Vahl Davies P.S. Larsen

University of New South Wales Technical University of Denmark
Australia Denmark
D.B. Murray A.C.M. Sousa
Trinity College Dublin University of New Brunswick
Ireland Canada
A.J. Nowak D.B. Spalding

Silesian University of Technology CHAM
Poland UK
K. Onishi J. Szmyd
Ibaraki University University of Mining and Metallurgy
Japan Poland
P.H. Oosthuizen E. Van den Bulck

Queen’s University Kingston Katholieke Universiteit Leuven
Canada Belgium
W. Roetzel S. Yanniotis
Universtaet der Bundeswehr Agricultural University of Athens
Germany Greece
B. Sarler
University of Ljubljana
Slovenia
Exergy Method
Applications
By
Jan Szargut
Exergy Method
Applications
Jan Szargut
Silesian University of Technology, Gliwice, Poland
Published by
WIT Press
Ashurst Lodge, Ashurst, Southampton, SO40 7AA, UK
Tel: 44 (0) 238 029 3223; Fax: 44 (0) 238 029 2853
E-Mail: witpress@witpress.com
http://www.witpress.com
For USA, Canada and Mexico
WIT Press
25 Bridge Street, Billerica, MA 01821, USA
Tel: 978 667 5841; Fax: 978 667 7582
E-Mail: infousa@witpress.com
British Library Cataloguing-in-Publication Data
A Catalogue record for this book is available

from the British Library
ISBN: 978-1-85312-753-3
ISSN: 1369-7331
Library of Congress Catalog Card Number: 2004113017
No responsibility is assumed by the Publisher, the Editors and Authors for any injury
and/or damage to persons or property as a matter of products liability, negligence or
otherwise, or from any use or operation of any methods, products, instructions or ideas
contained in the material herein.
© WIT Press 2005.
Printed in Great Britain by Athenaeum Press Ltd, Gateshead.
All rights reserved. No part of this publication may be reproduced, stored in a retrieval
system, or transmitted in any form or by any means, electronic, mechanical, photocopying,
recording, or otherwise, without the prior written permission of the Publisher.
Contents
Foreword xi
Preface xiii
Introduction xv
Nomenclature xvii
CHAPTER 1
Exergy balance and exergy losses 1
1.1. Definition of exergy and exergy losses ................................................ 1
1.2. Exergy balance and exergy efficiency .................................................. 4
1.3. Exergy and anergy ............................................................................... 9
1.4. Typical irreversible phenomena ........................................................... 9
1.5. Anthropogenic and natural exergy losses ......................................... 16
Exercises ........................................................................................................ 18
CHAPTER 2
Calculation of exergy 19
2.1. Types and components of exergy ...................................................... 19
2.2. Physical exergy .................................................................................. 20
2.3. Chemical exergy ................................................................................. 21
2.4. Enthalpy of devaluation ..................................................................... 34
2.5. Chemical exergy of organic fuels ....................................................... 35
2.6. Chemical exergy of solutions ............................................................. 37
2.7. Exergy of thermal radiation ................................................................ 38
2.8. Nuclear exergy ................................................................................... 41
2.9. Exergy losses in thermal plants .......................................................... 42
Exercises ........................................................................................................ 54
CHAPTER 3
Cumulative exergy consumption and partial exergy losses 57
3.1. Definition of the cumulative exergy
consumption (CExC) .......................................................................... 57
3.2. The problem of CExC of the human work ........................................... 58
3.3. A set of input-output equations ........................................................ 59
3.4. Cumulative exergy efficiency ............................................................. 60
3.5. Cumulative and partial exergy losses ................................................. 63
3.6. Net coefficients of consumption ........................................................ 64
3.7. Sequence method for the evaluation of
partial exergy losses ........................................................................... 67
Exercises ........................................................................................................ 72
CHAPTER 4
Practical rules for improving thermodynamic
imperfection 75
Exercises ........................................................................................................ 90
CHAPTER 5
Depletion of non-renewable natural resources;
thermo-ecological cost 91
5.1. Definition of the thermo-ecological costs .......................................... 91
5.2. Evaluation of the thermo-ecological cost of
deleterious waste products ................................................................ 91
5.3. Balance equations .............................................................................. 92
5.4. Influence of the interregional exchange ............................................. 93
5.5. Calculation of the thermo-ecological cost .......................................... 95
5.6. Sustainability index .......................................................................... 102
Exercises ...................................................................................................... 103
CHAPTER 6
Economic applications of exergy 105
6.1. Exergo-economics ............................................................................ 105
6.2. Optimization of the thermo-ecological cost ...................................... 108
6.3. Optimization of the exergetic cost .................................................... 114
6.4. Correction of the economic optimization ......................................... 115
6.5. Influence of thermodynamic imperfection on
the investment cost .......................................................................... 115
6.6 Evaluation of the natural mineral capital and
freshwater resources of the Earth .................................................... 116
Exercise ........................................................................................................ 119
CHAPTER 7
Application of exergy for determining the pro-ecological tax 121
7.1. Necessity of a new tax ..................................................................... 121
7.2. Structure of the pro-ecological tax ................................................... 122
7.3. Pro-ecological tax resulting from the use of
machines and installations ............................................................... 125
7.4. Burdening of imports and exports .................................................... 126
7.5. Discussion ....................................................................................... 127
Exercises ...................................................................................................... 128
Appendix 129
Solutions of exercises 143
References 153
Index 161
This page intentionally left blank
Foreword
It is a great pleasure, and an honour for me, to have the opportunity to write a
foreword to this latest monographic work by Professor Szargut. When I first met
him in person (in the 1980s) I had already got to know him through his work -
actually it is through one of his papers, (Brennstoff-Wärme-Kraft, v.19, n.6,
1967), that I became interested in the concept of exergy and in its possible
applications to the thermodynamic evaluation of industrial processes.
Throughout my academic years, I can honestly say that his work was a constant
stimulus and a consistent source of inspiration. There is no field of exergy
analysis that Jan Szargut has not contributed to - from the determination of the
exergy value of materials, to the definition of a rational performance parameter
(the exergetic efficiency), to the coupling of exergetic and economic
considerations in determining the “optimal” design or operating point of a
process or of a technological production chain, he has published an extensive
number of seminal theoretical works and innumerable applications. He has
worked (and often published) with most of the historical innovators of the exergy
field including, amongst others, Viktor Brodyanskyi, Wolfgang Fratscher,
Richard Gaggioli and Dominick Sama.
In my view, Professor Szargut’s most enduring contributions are his
fundamental work on the definition of a “standard reference environment”
(Chapter 2 and Appendices) and his great intuition about the Cumulative Exergy
Content (CEC, Chapter 3). The two are linked of course to each other, and all
present research in both fields is still in essence based on his work. The CEC has
proven to be a very fruitful tool, both for theoretical and practical reasons - it
constituted the first rational basis for a completely coherent evaluation method of
every energy- and material conversion process.
One of the great gifts of Jan Szargut is his scientific perseverance, by which I
mean his ability to further expand and deepen his own research. And this is very
clear in this book. The CEC was conceived as an “industrial” method, and since
his first introduction (in the 1980s), substantial advances, especially in the field
of Thermo-Economics, led to the agreement that the neglected environmental
externalities do play an important role in the definition of “optimal” designs.
Here we see that Szargut elaborated on his original concept, and, with a
remarkable intellectual effort presents it in such simple terms so as to make it
seem obvious, he further extends the CEC to account for the “depletion of the
non-renewable natural resources”. This is by no means a trivial task, but he
explains it here (Chapter 5) in an easy yet rigorous style, basing it all on
fundamental principles (Basic equations, Section 5.3).
From his early interests in the possible implications of the exergy analysis to
the problems of social economy, Professor Szargut developed an original version
of the otherwise well-known Exergo-Economics (Chapter 6), a theory that links
the irreversible losses (exergy destruction) to the capital costs associated with
their avoidance. Though the two of us do not agree here in our conclusions and
in some non-secondary details of the methodology, still I must admit that he
presents a very strong point for his side of the story. And he goes - again!- one
step further, when he develops (Chapter 7) a rational, complete and well-founded
proposal for a new system of taxation that takes into account not the monetary
income, but the “ecological cumulative burden” that a commodity (goods or a
service) places on the environment.
All of us who work in the field of Energy System Analysis owe something to
Jan Szargut, and I wish that the younger readers of this book, who cannot fully
appreciate this simple fact because they cannot put it in a proper historical
perspective, will take not only my word for this strong statement, but also that of
a large number of colleagues whose esteem for him has remained unchanged
through the years. As witnesses, if needed, I call on more than 200 papers he
published, and the large number of his former students who are all now leaders
in their respective fields.
A final word of warning - this book is not an easy read! If it seems so, read it
over, and you will appreciate, as I did, the somewhat hidden depth and wide
implications of virtually all of its fundamental statements. Read it over. And
over. And you will discover, as I did, that most of what you do now, Jan Szargut
did - or thought of - before. And he managed to do it, somehow, better.
With friendship, respect and gratefulness for what he has taught me until now,
and with the certainty to learn more from him in the future,
Enrico Sciubba
University of Roma 1, “La Sapienza”
Preface
The exergy method makes it possible to detect and quantify the possibilities of
improving thermal and chemical processes and systems. The introduction of the
concept “thermo-ecological cost” (cumulative consumption of non-renewable
natural exergy resources) generated large application possibilities of exergy in
ecology. The economy of non-renewable natural exergy is one of the most
important problems considered in the present book.
The book contains a short presentation of the basic principles of exergy
analysis and discusses new achievements attained in the last 15 years. The most
important new problems, discussed so far only in scientific journals, are:
calculation of the chemical exergy of all the stable chemical elements, discussion
of the global natural and anthropogenic exergy losses, practical guidelines for
improvement of the thermodynamic imperfection of thermal processes and
systems, development of the determination methods of partial exergy losses in
thermal systems, discussion on the thermo-ecological cost, a general method for
the optimization of the operational and design parameters aiming at the
minimization of the depletion of non-renewable natural resources, sustainability
index of the natural environment, evaluation of the natural mineral capital of the
Earth, application of exergy for the determination of a pro-ecological tax,
substituting the existing personal taxes.
The book assumes a knowledge of basic thermodynamics, and therefore, is
appropriate for graduate students and also for engineers practicing in the field of
energy and ecological management. The book may be also helpful in scientific
research.
The book has been prepared thanks to the support of the Institute of Thermal
Technology of the Silesian University of Technology (Gliwice, Poland), directed
by Prof A. ZiĊbik. I would like to express my gratitude to Prof Enrico Sciubba
(University “La Sapienza”, Rome, Italy) for his valuable suggestions for
improving the text of the book, and to Dr W. Stanek (Institute of Thermal
Technology, Gliwice) whose scientific results enriched the content of the book.
Jan Szargut
2005
Introduction
All kinds of human activities are supported by a consumption of natural

resources, both non-renewable and renewable ones. The exhaustion of non-
renewable natural resources is very dangerous for the future of humankind and
therefore a measure should be introduced to evaluate these resources, and
methods should be devised to estimate their exhaustion.
The ability of natural resources to run thermal, chemical and biological
processes, results from the deviation of their state and composition from the
thermodynamic equilibrium, with the prevailing components of the natural
environment. Hence, the ability to perform maximum work in the conditions of
natural environment can be accepted as a measure for the evaluation of natural
resources. The quantity defined in such a way has been termed exergy. This term
was introduced by Z. Rant [42], whose works began a very intensive
development in this field of technical thermodynamics.
Exergy analysis has been developed as a result of the application of the
second law of thermodynamics in investigations of the thermodynamic
imperfection of thermal processes. Forerunners of exergy analysis were G. Gouy,
A. Stodola, J.W. Gibbs and F. Bošnjakoviü. Gouy [23] and Stodola [55]
formulated independently the law determining the loss of the ability to perform
work due to thermodynamic irreversibility. Gibbs [22] introduced the concept of
maximum work of chemical reactions. Keenan [30] introduced the concept of
availability. Bošnjakoviü analyzed the deleterious impact of irreversibilities and
propagated the idea of “fighting” them [7].
During the decade 1960–1970, exergy analysis was developed mainly in
Europe, but after 1980 the interest in this analysis increased considerably in
America. The bibliography of exergy analysis contains thousands of papers,
among them many monographic books [104]. Among the authors of
monographic books the following ones may be mentioned: J. Szargut and R.
Petela [60]; I. Nerescu and V. Radcenko [39]; W.M. Brodyanskyi [9]; W.
Fratzscher W.M. Brodyanskyi and K. Michalek [19]; T.J. Kotas [31]; J. Szargut,
D.R. Morris and F. Steward [69]; W.M. Brodyanskyi, M.V. Sorin and P. Le Goff
[10].
Nomenclature
aij,auj coefficient of gross consumption of the major product of ith process or
of uth by-product, related to the complex of useful products of the
considered jth process, containing a unit of its major product
Aij coefficient of the net consumption of the major product of ith process
per unit of the major product of the considered jth process
A,a square matrix of the coefficients Aij, aij
B, b exergy of the stream of matter crossing the immovable system
boundary (total and specific), J; J/kg, J/mol
b* cumulative consumption of primary exergy per unit of the considered
product, J/kg, J/mol
Bm exergy of stream of matter crossing the movable system boundary, J
Bs exergy of the system, exergy of the matter contained within the system
boundary, J
c specific heat capacity, J/(kg·K), J/(mol·K)
c velocity related to the Earth’s surface, m/s
dij auxiliary consumption coefficient, taking into account the import of
semi-finished products per unit of the jth major product
Di,Dr monetary value of the ith exported and rth imported product,
E unitary diagonal matrix
fij coefficient of by-production of the substituted major product of ith
process per unit of the major product of the considered jth process
fuj coefficient of production of the uth by-product per unit of the major
product of the considered jth process
f square matrix of the coefficients fij
g gravitational acceleration, m/s2
G, g Gibbs free energy (total and specific) J; J/kg, J/mol
Gj annual production of the jth product
fG standard free energy of formation at normal temperature, J/kg, J/mol
H, h enthalpy (total and specific) J; J/kg, J/mol
HL,HH lower and higher heating value J/kg,
mi molarity of the ith component of solution, mol/kg H2O
mij amount of the ith machines or installations applied in the jth production
process,
M molecular mass, kg/kmol, g/mol
(MHL) lower heating value of gaseous fuels, J/mol
n substance amount, mol
N electric power
p pressure, Pa
pkj amount of the kth aggressive component of waste products rejected to
the environment per unit of the jth major product
Pk annual production of the kth aggressive component of waste products
rejected to the environment in the considered region
Pr Prandtl number
Q amount of heat, J
r velocity related to the system boundary, m/s
r annual rate of discount
R gas constant, J/(kg·K), J/(mol·K)
Re Reynolds number
s velocity of the system boundary related to the Earth’s surface, m/s
ssu replacement ratio in units of the sth substituted major product per unit of
the uth by-product
S, s entropy (total and specific) J/K; J/(kg·K), J/(mol·K)
SNkj net cumulative consumption of the kth semi-finished product per unit of
the jth product
T temperature on thermodynamic scale, K
V, v volume (total and specific), m3; m3/kg, m3/mol
wk monetary coefficient of ecological damages per unit of kth aggressive
waste product, $/kg, $/mol
W mechanical work, J
x quality of saturated vapor
X height, m
yi molar fraction of the ith species in a solution
zi mass fraction of ith species in a solution
j immediate gross consumption of primary exergy per unit of the jth
product, together with its by-products, J/kg, J/mol
Nj immediate net consumption of primary exergy per unit of the jth
product, J/kg, J/mol
b* cumulative exergy loss burdening all the links of fabrication of the
considered product
i activity coefficient, (molarity scale)
 symbol of loss (B = exergy loss, p = pressure loss)
 symbol of increase (B = exergy increase, T = temperature increase)
B exergy (exergetic) efficiency
E energy efficiency
j specific thermo-ecological cost of the jth product, J/kg, J/mol
m thermo-ecological cost of the exported products, per monetary unit,
J/$
k cumulative exergy consumption of non-renewable resources due to the
emission of unit of kth waste product, J/kg, J/mol
i life time of the ith machine or installation operating with rated
capacity, years
 pro-ecological tax
Subscripts
a output
B related to exergy
ch chemical
d input
D driving
E related to energy
el related to electricity
f friction
F fuel
i,j,k,p order number of the process and its major product
i internal
m mechanical
m moving
n standard, conventional
N net value (per unit of the major product),
nu nuclear
ph physical
q related to the heat source
s related to the system
u useful
u order number of the by-product
w waste
0 ambient, related to the reference level
Superscripts
 standard state at normal temperature
. dot above the symbol denotes a quantity related to the time unit
–
dash above the symbol denotes a local (differential) value
*
cumulative quantity
Abbreviations
CExC cumulative consumption of primary exergy
CExE cumulative exergy efficiency
CExL cumulative exergy loss
DCP domestic consumption product, $/year
HP-plant heat-and-power plant
LNG liquid natural gas
NLUE natural losses of utilizable exergy
PExL partial exergy loss
VAT value added tax
Chapter 1
Exergy balance and exergy losses

1.1. Definition of exergy and exergy losses
In fig. 1.1 a hydraulic and a thermal power plant are compared. The hydraulic
plant exploits the difference between the levels of water in the upper and lower
reservoir. Similarly, a thermal plant exploits the temperature difference between
the hot heat source and a cold heat sink. There is, though, a great difference
between the two plants: the hydraulic one can (neglecting viscous and mech-
anical friction) convert into work the total potential energy of water taken
from the upper reservoir. However, as Carnot discovered (1824), a thermal
power plant (even operating without any losses) can convert into work only
a portion of the heat taken from the hot source. The law of Carnot has
the form:
T1 T 2
W =Q (1.1)
T1
Figure 1.1: Comparison of a hydraulic and thermal power plant.

2 EXERGY METHOD: TECHNICAL AND ECOLOGICAL APPLICATIONS
where T1 and T2 are the absolute temperature values of the hot source and the
cold sink.
The heat from the hot source can be best utilized if a natural (“free” and
practically unlimited) cold sink can be used. The natural environment represents
such a heat sink or source. Hence, the “quality” of heat is not constant; it de-
pends on both the absolute temperatures of the heat source and of the natural
environment. This quality can be expressed by means of the maximum ability to
perform work between the two given heat reservoirs:
T T0
W max = Q (1.2)
T
where T0 = absolute ambient temperature

(T–T0)/T = dimensionless Carnot-factor characterizing the quality of heat taken
from the source with a constant temperature.
The amount of the performed work can exceed the value resulting from
eqn (1.2), only if an artificial heat sink is used, which must, be created and
maintained by means of other valuable kinds of energy.
Equation (1.2) applies only to ideal reversible processes. According to the
second law of thermodynamics, all real processes are irreversible. In real pro-
cesses, the amount of performed work is always smaller than that resulting from
eqn (1.2). Hence, eqn (1.2) characterizes the maximum attainable amount of
performed work.
Particular kinds of energy differ also in their ability to be transformed into
other kinds of energy. For example, internal energy can be only partially trans-
formed into mechanical energy (kinetic or potential) or into mechanical work.
It is worth stressing that the ability of some streams of matter to drive thermal
processes (for example, the stream of compressed air) cannot be characterized
in terms of energy (the energy of compressed air at ambient temperature equals
the energy of atmospheric air).
The ability to perform mechanical work has been accepted as a measure of
the quality of various kinds of energy, characterizing their ability to be trans-
formed into other kinds of energy. This ability depends not only on the com-
position and state parameters of the considered matter (determining its energy),
but also on the composition and state parameters of the matter commonly
appearing in the environment in which the considered transformation process
takes place. The mentioned environmental parameters should determine the
reference level for the calculation of the discussed quality index.
This quality index for energy has been termed by Z. Rant [42] exergy. It
expresses the maximum work output attainable in the natural environment, or
a minimum work input necessary to realize the reverse process. A second
version proposed by Riekert [47] is very convenient and can be formulated as
follows:
Exergy expresses the amount of mechanical work necessary to produce a
material in its specified state from components common in the natural environ-
ment, in a reversible way, heat being exchanged only with the environment.
EXERGY BALANCE AND EXERGY LOSSES 3
In comparison to energy (which is a function of the state of the considered

matter only) exergy is a function of the state of the considered matter and of the
common components of the environment.
Exergy does not satisfy a law of conservation. Every irreversible process
causes an irrecoverable loss of exergy GB, which can be determined by means of
the Gouy-Stodola law [23, 55]:
įB = T0 6'S (1.3)
where T0= environmental temperature

6'S = sum of the entropy increase values of all the kinds of matter taking
part in the process.
As Sama [48] has stated, some degree of exergy loss has to be accepted
to reduce the capital investment. For example, a smaller heat transfer area
in a heat exchanger can be attained for a higher temperature difference
between the heating and the heating fluid in every point of the heat transfer
surface. But any temperature difference during the heat transfer generates
an exergy loss. Hence, accepting exergy loss should always have some econ-
omic justification. If such a justification does not exist, it indicates that the
exergy loss results only from an error in the art of engineering.
On the other hand, every exergy loss causes a decrease of the useful
effect of the process or an increase in the consumption of its driving means
(if the required useful effect is given). Hence, the presence of an exergy loss
always indicates the possibility of a thermodynamic improvement of the
process, but the profitability of such an improvement should be checked by
means of an economic analysis (because this is usually connected with some
increase of capital investment).
Exergy losses can be divided into internal and external ones. Internal
exergy losses are connected with the internal parts of the system; they appear
inside the control boundary of the system and can be easily calculated by
means of eqn (1.3). External exergy losses result from the discharge of waste
products of the process into the environment. The exergy of waste products
is destroyed in the environment. Hence, the external exergy loss equals the
exergy of the considered waste product. The calculation of external exergy
losses by means of eqn (1.3) is difficult; it is easier to determine them by
means of the exergy of waste products. External exergy losses indicate that
the primary causes of exergy losses often act far from the place where the
exergy loss appears. It may be difficult to decide which is the primary cause
of an exergy loss. For example, the external exergy loss when combustion
gases flow out of the boiler can be interpreted as a result of irreversible
phenomena inside the boiler or as the result of the absence of their utiliza-
tion behind the boiler.
Internal exergy losses can be divided into technical and structural ones
[9]. Technical exergy losses result from the technical imperfection of parts
of the installation, and can be decreased by improving the performance of
the relevant components. Structural exergy losses cannot be substantially
diminished without changing the structure or principle of the process. For

example, if the heat capacities of the fluid streams in a heat exchanger
differ, the temperature gap between these streams differs in each single
cross-section of the heat exchanger and cannot be eliminated even if an
infinitely large heat transfer area is used.
The main task of exergy analysis is to detect and to quantify the cau-
ses of thermodynamic imperfections. These causes are characterized by
connected exergy losses.
1.2. Exergy balance and exergy efficiency
Exergy is exempt from the law of conservation, so that the exergy balance must be
closed by the internal exergy loss [56]:
B d = ' B s + 6 ' B q + B a u + B a w +W + G Bi (1.4)
where Bd= exergy delivered to the system with the streams of matter
Bau, Baw = exergy carried out from the system by useful products and waste
products
'Bs = increase of exergy of the system
'Bq = increase of exergy of the head source being in contact with the
system
W = work performed by the system
GBi = internal exergy loss, due to irreversibilities inside the system.
Exergy carried away with waste product constitutes the external exergy
loss.
The exergy increase of the external heat source can be determined by
means of the Carnot factor:
T T0
'Bq = Q (1.5)
T
where Q = heat extracted from the external heat source
T= temperature of the heat source (measured at the system boundary).
For steady-state processes, in which the flow velocities, chemical com-
position and thermal parameters are constant at all points of the system, the
exergy of the system remains constant and the exergy balance can be expressed
as a time rate of the components:
B d = B au + B aw + 6'B q + W + įBi (1.6)
where the dotted terms denote quantities per unit time.

The exergy balance can be presented in the form of a flow diagram, fig.
1.2. This diagram was introduced by Szargut [56] in 1956 and by Grassmann
Figure 1.2: Flow diagram of the exergy balance.
[24] in 1959. The width of the arrows is proportional to the exergy values. The
width of the band of the internal exergy loss increases inside the system
boundary from zero to the value resulting from eqn (1.3).
The exergy balance can also be presented together with the energy
balance in a common flow diagram, fig. 1.3 [3]. The arrows with thick lines
represent the energy flows. The hatched arrows represent the exergy flows, and
the crosshatched areas—the exergy losses.
Figure 1.4 presents combined flow diagrams of simplified typical heat
machines. No exergy flow is associated with the heat rejected to the environ-
ment. The work delivered by the prime mover is smaller than the driving
heat. The heat delivered to the heated room by the heat pump is greater than
Figure 1.3: Common flow diagram of energy and exergy balances of a steady-
state flow process.
Figure 1.4: Common flow diagrams of energy and exergy balances for simple
heat machines.
the driving work, but the delivered exergy is very small. In a refrigerator the
flow of the useful heat extracted from the refrigerated room and of the exergy
delivered to this room have opposite directions.
The ratio of the useful exergy effect to the consumption of the driving
exergy constitutes the exergy efficiency, also called rational efficiency or
effectiveness:
Bau Bdr + 'Bsu + Ȉ'Bqu +Wu

ȘB = (1.7)
BD Ȉ'BqD WD
where BD, Bdr= exergy of the delivered driving materials (for example, fuels) and of
the non-driving raw materials
'Bsu= useful exergy increase of the system

–'Bsu, 'Bqu= exergy decrease of the source of driving heat and increase of the
serviced source of heat
WD,Wu= driving work and useful performed work.
The exergy efficiency is always smaller than unity. In some processes its
value is negative. For example the cooling tower of the steam power plant does
not produce any positive exergy effect and its exergy efficiency calculated
by means of eqn (1.7) would be negative. In such cases the degree of thermo-
dynamic perfection Kp can be calculated to characterize the irreversibility of the
process. It can be defined as the ratio of the useful exergy output to the exergy
input. When calculating Kp the transit exergy should be omitted [9]. It comprises
the exergy components not taking part in the thermodynamic changes (for
example, the chemical exergy of the solvent when analyzing chemical processes
in solutions).
Example 1.1. The exergy efficiency of a thermal prime mover can be

determined as the ratio of the performed mechanical work to the exergy
decrease of the source of driving heat. Hence, it expresses the ratio of the
energy efficiency of the considered prime mover to the energy efficiency of
a Carnot machine:
W T Ș
ȘB = = E (1.8)
QD T T0 ȘE max
where QD= driving heat, T = the temperature of the source of driving heat.
Similarly, the exergy efficiency of a compressor heat pump absorbing the
bottom heat from the environment can be determined as the ratio of the exergy
increase of a heated room to the driving mechanical work. Hence, it expresses
the ratio of the coefficient of performance COP of a real heat pump to COPmax of
the Carnot heat pump:
Qu Tu T0 COP
ȘB = = (1.9)
WD Tu COPmax
where WD = driving work, Qu = useful heat, Tu = the mean temperature of the

carrier of useful heat, COP = Qu/WD.
Equation (1.9) should not be applied if the bottom heat is not taken from the
environment. The exergy drop of the bottom heat source should be taken into
account, according to the definition, eqn (1.7):
Qu Tu T0 COP Tu T0
ȘB = = (1.10)
Tb T0 Tu T0 Tu
W D + Qb COP + ( 1 COP )
Tb Tb
where Qb = heat extracted from the bottom source, Tb = temperature of the bottom
source.
Example 1.2. In a complex (multi-purpose) process, the ratio of the energy

efficiency of a real process to that of a reversible process does not usually
express the exergy efficiency because the proportion of the useful effects in the
real process differs from that in the reversible process. For example, the internal
exergy efficiency of a heat-and-power plant producing useful mechanical work
Wu and useful heat Qu is expressed as follows:
Tu T0
Wu + Qu
Tu
ȘB i = (1.11)
T T0
QD
T
where the symbols: see eqns (1.8) and (1.9).

The influence of the exergy losses appearing in particular parts of the
process on its useful effect Bu may be examined by means of the coefficients of
sensibility:
wBu wK
Vk = = B (1.12)
w(įBk ) wH k
where GBk,Hk = total and relative exergy loss in the kth part of the process.
The application of sensibility factors can be illustrated by the analysis
of a chain process comprising three links. The first link is fed with the
driving exergy BN, the third one delivers the useful effect, which can be
expressed as:
Bu = BN ȘB1 ȘB 2 Ș B 3 (1.13)
Exergy losses in the individual links are
įB1 = BN (1 ȘB1 ), įB2 = BN Ș B 1 (1 ȘB 2 ), įB3 = BN Ș B 1 ȘB 2 (1 ȘB 3 ) (1.14)
At constant exergy efficiency values of each link, we can express the co-
efficients of sensibility as follows:
V 1 = ȘB 2 ȘB 3 , V 2 = ȘB 2 , V 3 = 1. (1.15)
Hence, the influence of particular exergy losses increases in the course of the
processes. It is smallest at the beginning of the chain of processes, and
largest at the end.
1.3. Exergy and anergy

Exergy is sometimes defined as a transformable part of energy (Rant [43],
Baehr [3]). This definition is unsatisfactory because of quite different fea-
tures of energy and exergy. For example, energy may be calculated from an
optional reference level. Only one requirement should be fulfilled: the as-
sumed conventional reference level should be the same for all portions of
matter taking part in the considered process. The reference level of exergy
is determined by the parameters of the natural environment. A degree of
some convention appears also in this case, but it is small and exactly
quantifiable (for example, the assumption of the conventional normal
ambient temperature, required in some cases). A negative value of energy
does not have any essential meaning. For example, the chemical enthalpy
calculated by means of the enthalpy of formation is usually negative. On
the other hand, a negative value of physical exergy means that the analyzed
state cannot be attained without a consumption of driving exergy.
As a consequence of the cited definition of exergy, Rant [43] and Baehr
[3] introduced a concept of anergy, defined as a non-transformable part of
energy. Hence, energy is the sum of exergy and anergy. The reference level
of anergy is optional, similarly as that of energy. Hence, anergy can be
negative. It would be very difficult to explain the physical meaning of a
negative value of anergy. The use of the concept of anergy is very incon-
venient when the temperature of the considered portion of matter is lower
than the ambient one. In this case, the extraction of some amount of energy
from this matter (for example, by refrigeration) causes an increase of its
exergy and decrease in anergy. Hence, the interpretation of exergy as a part
of energy is not logical. Therefore, the discussed definition of exergy and the
concept of anergy are not used in the present book.
1.4. Typical irreversible phenomena
1.4.1. Friction
The main causes of exergy losses are friction, heat transfer with a finite tempe-
rature gradient, throttling, diffusion, combustion and other chemical reactions. For
example, the exergy loss due to the mechanical or hydraulic friction can be
expressed as follows:
T0
įB = Q f (1.16)
T
where Qf = heat of friction

T = temperature of the body absorbing the heat of friction.
Figure 1.5 presents an irreversible adiabatic expansion. The area under the curve
represents the heat of the hydraulic friction absorbed by the working fluid. The
Figure 1.5: Heat of friction and exergy loss in an adiabatic flow machine.
sum of the entropy increments is expressed by the difference s2–s1. Hence, the
exergy loss is represented by the area of the rectangle below the line of the
ambient temperature. It is larger than the heat of friction when the temperature of
the body absorbing the heat of friction is lower than the ambient one. This effect
appears in refrigerators. The hydraulic friction during the flow of the chilling
fluid not only decreases its refrigeration ability but also increases the demand for
compression work.
1.4.2. Irreversible heat transfer
The exergy loss due to the irreversible heat transfer is given by the formula:
T1 T2
d(į B ) = d Q T0 (1.17)
T1 T2
where dQ= elementary amount of transferred heat

T1,T2= temperature of the bodies exchanging heat (the warmer and the
colder one).
The lower the temperature in the process, the greater is the deleterious in-
fluence of irreversibility. On the other hand, the higher the temperature in the
process, the larger are the admissible temperature differences in the heat transfer
processes. Therefore, in metallurgical ovens the temperature difference between
the heating gases and the heated body may amount to some hundred degrees, but
in condensers of steam turbines or refrigerators it is not larger than few degrees.
Example 1.3. The thermal power of a heat pump is 10kW. Its driving
electric power is 2.85kW. The mean temperature of the heating fluid is 323K,
and of the heated room 293K. The ambient temperature is 273K.
According to eqn (1.9) the minimum driving power N d min of the heat pump in
the considered conditions would be:
10 u 20
N d min = = 0.68kW .
293
Hence, a considerable part of the real driving electric power (2.17kW) is lost due
to the irreversible course of the processes connected with the operation of the heat
pump. One of the important sources of exergy losses is the irreversible heat transfer
between the heating fluid and the heated room. The exergy loss due to this
irreversible heat transfer is
10 u 30 u 273
įB = = 0.86kW
323 u 293
Hence, the considered exergy loss (which can be interpreted as a loss of driving
electric power) amounts to 30% of the driving power.
The temperature distribution in heat exchangers is usually analyzed by
means of the diagram enthalpy stream—temperature (fig. 1.6a). It is convenient
to introduce the exergy temperature defined as follows:
T
ș =1 0 (1.18)
T
In the diagram enthalpy stream-temperature in the exergy scale (fig. 1.6b)
the area between the curves of the heating and the heated medium represents the
exergy loss due to the irreversible heat transfer, according to the formula:
Figure 1.6: Temperature distribution and exergy loss in a heat exchanger.

§ 1 1 ·
d(į B ) = d Q T0 ¨ = d Q ( șh șc ) (1.19)
© Tc Th ¸¹
where Th, Tc, Th, Tc are the exergetic and the absolute temperature of the hot and
cold fluid.
1.4.3. Throttling
Throttling is a particular case of irreversible adiabatic expansion (the performed

work is equal to zero). The elementary exergy loss can be expressed as follows:
T0
d(įB ) = V dp (1.20)
T
where V is the volumetric flow rate of the fluid.

The application of eqn (1.20) to an ideal gas indicates that the exergy loss
due to its throttling is independent of its temperature:
p1
įB = n RT0 ln (1.21)
p2
where n denotes the molar flow rate of the gas.
1.4.4. Diffusion
Diffusion appears in many technical and natural processes. In the simplest

case of diffusion the initial temperature and pressure of two solutions is the
same, but the chemical composition is different. The adiabatic mixing of
these solutions is irreversible. It is impossible to separate the final solution
so as to restore the initial state without some consumption of exergy. The
exergy loss due to diffusion expresses the minimum work required to restore
the initial state. In the case of two ideal solutions (denoted as 1 and 2) with
the same initial temperature and pressure the exergy loss due to diffusion
can be expressed as follows:
ª º
įB = RT0 «(n1 + n2 ) ¦ yi lnyi n1 ¦y i1 lnyi1 n2 ¦y i2 lnyi 2 » (1.22)
¬ i i i ¼
where yi = molar fraction of the ith component

n1, n2 = number of moles of the mixed solutions.
Example 1.4. The oxygen-enriched blast delivered to a blast furnace
(containing 30% O2 per mole) is produced by mixing technical oxygen (con-
taining 95% O2 per mole) with atmospheric air (21% O2 per mole). The con-
sumption of technical oxygen per mole of the enriched blast results from the
balance of oxygen:
y B = 0.95 nx + 0.21(1 nx )
where nx = consumption of technical oxygen, in moles per mole blast, yB = molar

fraction of oxygen in the enriched blast.
From the oxygen balance it results that nx = 0.122. From eqn (1.22) results
the exergy loss due to the irreversible mixing of technical oxygen with
atmospheric air. Assuming T0 = 290K we obtain:
290u8.3143[0.3 ln 0.3+0.7 ln 0.7 – 0.122(0.95 ln 0.95+0.05 ln 0.05)

–0.878(0.21 ln 0.21+0.79 ln 0.79)] = 326.4kl/kmol
The calculated value expresses the loss of driving exergy that would appear if
the production of technical oxygen were reversible. In real processes the loss of
driving exergy would be considerably greater. The technology of the imme-
diate production of enriched blast is known, but as yet it is too expensive.
1.4.5. Combustion
Combustion is a complex process composed of several irreversible steps:

mixing of the fuel with the oxidizer (diffusion of oxygen), chemical reaction,
heat transfer from reacting molecules to other molecules, mixing of com-
bustion products with the remaining part of combustion gases (diffusion).
Usually, combustion runs simultaneously with heat transfer to the walls of
the combustion chamber.
The total exergy loss in an adiabatic and isobaric combustion process
represents a considerable part of the fuel exergy. Figure 1.7 presents an
exergy analysis of the adiabatic and isobaric combustion of elementary coal,
the air ratio being stoichiometric [60]. The area below the isobar 3–4 of
combustion gases represents the heating value of the fuel, and that between
the isobar 3–4 and the environmental isotherm—the physical exergy of
combustion gases. Point 1 represents the state of the combustion reactants
(fuel + air), and point 2 of the combustion products in equilibrium with the
environmental air. The area under 1–2 represents the chemical exergy of
fuel, and under 1–5 the total exergy loss in the adiabatic combustion pro-
cess. The total exergy loss amounts to 124 840 kJ/kmol C (38.4% of the
chemical exergy of fuel). The total exergy loss increases with the oxidizer
excess. Point 4c represents the state of combustion gases after the thermal
dissociation of CO2. After the temperature of combustion gases has been
lowered, their state returns to the isobar 3–4. The additional exergy loss due
to dissociation is small.
Lior [35] analyzed the components of the exergy loss due to the particular
steps of the combustion process. He came to the conclusion that the exergy loss
due to the chemical reaction of oxidation is relatively small, and amounts only to
about 5–6% of the chemical exergy of fuel, constituting about 15–18% of the
total exergy loss. Mixing the combustion reactants causes 8–10% of the total
exergy loss. The main cause of exergy loss is the internal heat exchange (72–
77% of the overall exergy loss).
The exergy loss in an adiabatic combustion process can thus be reduced by
preheating the combustion reactants. As shown in fig. 1.8 the enthalpy increase
of combustion gases equals that of the reactants, while the entropy increase of
combustion gases is smaller than that of combustion reactants. Therefore, the
total exergy loss becomes smaller.
1.4.6. Absorption and emission of thermal radiation
The absorption of thermal radiation on a solid surface is always connected with

the emission of thermal radiation from the surface. The simultaneous absorption
and emission of thermal radiation are irreversible if the temperature values of the
emitting and absorbing surfaces are different [40].
The energy flux Ơb associated with the thermal radiation of a black surface is
E b = A ı T = Aeb
4
(1.23)
where A= area of the emitting surface,
V= 5.667 u 10–8 W/(m2 K4) the Stefan–Boltzmann constant,
eb = density of the energy flux of thermal radiation.
Figure 1.7: Exergy loss in an adiabatic Figure 1.8: Influence of the preheating
and isobaric combustion of combustion reactants on
process of elementary coal. the exergy loss in adiabatic
combustion of elementary
coal.
When considering the thermal radiation of a closed surface, the density of

the energy flux of thermal radiation is inversely proportional to the second
power of the distance from the emitting surface.
The entropy flux associated with the stream of black surface radiation is
4 4 E b
Sb = A ı T 3 = (1.24)
3 3 T
In order to calculate the energy flux of the radiation of a gray surface, eqn
(1.23) should be multiplied by the surface emissivity H. Eqn (1.24) can be
also multiplied by the emissivity of a gray surface, but only when the
emissivity does not depend on the wave length.
Example 1.5. The energy flux of solar radiation over the atmosphere is
eSE = 1.395 kW/m2. The density of the energy flux decreases with the
second power of the distance from the Sun. Hence, near the Earth, above its
atmosphere the density of the energy flux of solar radiation is:
2 2
§ R· § 695 500 ·
eSE = eS ¨ ¸ = ı TS4 ¨
© L¹ © 149 500 000 ¸¹
where R = radius of the Sun, L = distance from the Sun surface to the Earth.
After introducing the value of eSE the equivalent temperature of the Sun’s
surface can be calculated: TS = 5807 K, if its emissivity is H = 1.
Entropy generation connected with a simultaneous emission of thermal
radiation of a black surface and absorption of a stream of radiation of another
black body contains a negative component expressing the entropy of absorbed
radiation and two positive components expressing the entropy of the emitted
radiation and the entropy increase of the heat sink represented by the absorption
surface due to the absorption of heat [40].
Considering two parallel black plates we obtain, per unit of the absorption
surface:
ª4 T 4 Ta4 º

¦ ' Sa = ı « Ta3 Te3 + e »
¬3 Ta ¼
(1.25)
ª1 § T 4· º
= ı « Ta3 + Te3 ¨ e ¸ »
¬3 © Ta 3 ¹ ¼
where Te and Ta are the absolute temperature values of the emitting and absorbing
surface.
In order to calculate the exergy loss due to the simultaneous absorption and
emission of thermal radiation, eqn (1.25) should be multiplied by the ambient
temperature.
Example 1.6. The temperature of the emitting surface can be higher or lower
than that of the absorbing surface. Let us consider a system of two parallel black
plates with the temperature values T1 = 1500K, T2 = 500K. The ambient
temperature is T0 = 300K.
When considering the first plate it should be assumed that T1 = Ta, T2 = Te.
From eqns (1.24) and (1.3) it results į b 1 = 17 kW/m2.
When considering the second plate, we should introduce T1 = Te, T2 = Ta. In
this case we obtain į b 2 = 96.3 kW/m2. In both cases the exergy loss is positive.
The sum of the calculated exergy losses expresses the total exergy loss appearing
in the considered system, that is in accordance with eqn (1.17).
1.5. Anthropogenic and natural exergy losses

Besides exergy losses derived from human activity, huge losses within the
Biosphere result from the irreversibility of natural phenomena (the absorption of
solar radiation, the emission of thermal radiation, the irreversible heat transfer
from inside the Earth to its surface and the braking of the planetary motion). The
irreversible absorption of solar radiation and emission of infrared radiation
constitute the prevailing part of these losses.
It is worth stressing that natural exergy losses are the main cause of the
formation of the non-equilibrium natural environment [87]. According to the
laws of non-equilibrium thermodynamics, irreversible phenomena can be
accompanied by coupled processes partially decreasing the effects of irrever-
sibility. These coupled processes can lead to the formation of stationary dis-
sipative structures, for example biological living structures.
Hence, the huge natural exergy losses connected with solar radiation, are the
very cause of the existence of life on Earth.
Exergy losses occurring within the zone of human existence, located near the
Earth’s surface, represent the most accessible natural resources of renewable
exergy. These losses may be distinguished by the term “natural losses of utili-
zable exergy NLUE” [88]. Every utilization of these resources denotes a shift of
exergy losses from the sphere of natural to the sphere of anthropogenic exergy
losses. For example in hydro-power plants about 1 TW (1012 W) of natural
exergy losses is shifted into the zone of anthropogenic ones.
The energy power of solar radiation reaching the upper layer of the Earth’s
atmosphere is about 174,000 TW [52]. From this radiation about 30% is
reflected by upper layers of the atmosphere (without any exergy loss), about 20%
is absorbed in the atmosphere and re-emitted in the form of infrared radiation,
about 24% of this energy warms the surface of continents and oceans (about
0.5% of this quantity is transformed into the exergy of wind, waves and sea-
currents [27, 36]. About 23% of the total solar radiation is used for the
evaporation of water (about 0.4% of this quantity is transformed into the
potential exergy of water droplets in clouds, then about 0.012% into potential
exergy of water in rivers). About 0.02% of the total stream of solar radiation
(energy about 40 TW, exergy about 37 TW) is absorbed by plants and partially
transformed into their chemical energy (energy about 2.5 TW, exergy about 2.9
TW) [21]. About 1 TW of the chemical energy of plants is used by humankind
for its needs. From the energy power of solar radiation reaching the Earth’s
surface (87 000 TW after Smil [52]) about 10% are reflected, and only a very
small fraction is accumulated in the form of natural resources (for example, in
the form of peat). Almost the total amount of the absorbed solar radiation is,
after numerous transformations, emitted again in the form of infrared radiation.
As a result of the greenhouse effect, a considerable flow of radiation
circulates between the Earth’s surface and the atmosphere. Therefore, the
total energy flow of the radiation absorbed by the Earth’s surface (equal to
the emitted energy flow of infrared radiation, amounting to 181,000 TW) is
larger than the immediately absorbed energy flow of solar radiation [26].
Assuming a mean emissivity of the Earth’s surface equal to 0.9 we can
calculate its mean equivalent temperature (289K).
The energy flow of the secondary radiation of the atmosphere amounts to
102,700 TW [26]. Hence, the energy stream of the radiation reaching the Earth’s
surface amounts to 114,100 TW. From this quantity results the equivalent
temperature of the upper layers of the atmosphere (251K).
In order to calculate the natural losses of the utilizable exergy connected
with the absorption of solar radiation and the emission of infrared radiation, the
entropy balance of the Earth’s surface should be formulated, under steady state
conditions:
4 § E E E ·
¦ 'S = S0 SS Sa Sr = ¨ 0 S a ¸ Sr (1.26)
3 © T0 TS Ta ¹
where:
S0 , SS , Sa , Sr = entropy flow of own infrared emission, absorbed solar radiation,
absorbed secondary radiation of the atmosphere, and relict
radiation of the cosmic space
E 0 , E S ,E a = energy flow of the mentioned kinds of radiation.
The relict radiation (remaining after the Big Bang) has a spectral
composition corresponding to the temperature 2.73K. The energy flow of the
Earth’s surface radiation transmitted immediately to the cosmic space
amounts to 7000 TW [26]. The corresponding flow of relict radiation rea-
ching the Earth’s surface amounts to 5.6u10–5 TW. Its entropy flow is very
small and may be neglected. It has been assumed that the accumulation of
energy near the Earth’s surface is very small. From eqn (1.26) we obtain the
sum of natural exergy losses burdening the absorption and emission on the
Earth’s surface:
¦ 'S = 272 TW / K, į B = 78.500 TW

The calculated sum of NLUE is greater than the exergy of the solar radiation
absorbed by the Earth’s surface. The remaining part of the con-sidered losses
results from the irreversible radiation exchange between the Earth’s surface and
the cosmic space.
Natural exergy losses may be compared with the effects of human
activity. The energy power of chemical and nuclear fuels extracted from
natural resources is about 12 TW. (About 6 TW of the chemical energy of
fuels and 1 TW of nuclear energy are used for the production of electricity
[52].) This power is almost totally destroyed in irreversible production and
consumption processes. Only some small part remains accumulated in buil-
dings, machines and installations, but their exergy is continuously destroyed
by corrosion and weathering. Additional losses of exergy appear in anthro-
pogenic processes of the consumption of plants. The estimated sum of
anthropogenic exergy losses per time unit is about 13 TW. Hence, they are
about 6,000 times smaller than the NLUE. This proportion reflects the scale
of the available natural exergy resources.
Exercises
1.1. Calculate the exergy efficiency of the prime mover if its energy
efficiency amounts to KE = 0.388. The temperature values of the feeding heat
source and the environment are Tf = 850K, T0 = 283K.
1.2. The prospectus of an industrial compressor heat pump gives the ratio of
the useful heat to the consumption of driving electricity 3.9 if the temperature of
the environment (the source of bottom heat) is T0 = 258K and of the heated room
Tu = 350K. Check the credibility of the information given.
1.3. The irreversibilities in a considered Carnot prime mover result only
from the temperature differences between the heat sources and the working fluid.
The temperature values of the feeding heat source and of the environment are Tf
= 900K, T0 = 300K. The temperature differences are 'T = 20K. The power of the
prime mover is 10 MW. Calculate the rates of exergy losses.
1.4. A stream of pure CO2 with ambient temperature and pressure mixes
with atmospheric air. The atmospheric parameters are T0 = 283K, p0 = 0.1MPa.
The partial pressure of CO2 in the atmosphere amounts to 33 Pa. Calculate the
exergy loss due to the irreversible mixing per 1kg of CO2 . Assume that CO2 has
the properties of an ideal gas.
1.5. A piece of ice (1kg) with the initial temperature T1 = 263K melts, and
the obtained liquid water reaches the ambient temperature T0 = 293K. The
specific heat capacities of ice and liquid water are ci = 2.14 kJ/(kg K), cw = 4.18
kJ/(kg K); the enthalpy of melting is L = 333.4 kJ/kg. Calculate the exergy loss
due to the irreversibility of the process.
Chapter 2
Calculation of exergy
2.1. Types and components of exergy
Exergy of a stream of matter crossing an immovable system boundary (flow exergy)

is a principal quantity appearing in exergy balances. This quantity can be divided
into its components, the most important being: kinetic exergy, potential exergy,
physical exergy bph, chemical exergy bch and nuclear exergy bnu [56]. Kinetic exergy
should be calculated by means of the velocity c related to the Earth’s surface.
Potential exergy should be determined by means of the height X above the lowest
level prevailing near the considered device. Per 1kg of the considered substance, we
obtain:
c2
b gX bph bch b nu (2.1)
2
where g is the gravitational acceleration.
The exergy Bs of the substance contained within the system boundary (internal
exergy) differs from flow exergy (of the substance stream crossing the system
boundary), like the enthalpy from the internal energy [56]:
Bs B V ( p p0 ) (2.2)
where V = volume of the considered part of the system

p, p0 = pressure of the considered substance and of the atmospheric air.
Exergy of the substance stream crossing a moving system boundary (with a
constant linear velocity s) is
s
Bm B V ( p p0 ) (2.3)
r
where r is the velocity of the substance stream related to the system boundary.
In eqn (2.3) it has been assumed that the direction of the velocity s is opposite
to that of the velocity r.
2.2. Physical exergy
Physical enthalpy, entropy and exergy are calculated from the state determined
by the ambient temperature T0 and pressure p0 without any change of the
chemical composition of the considered substance. The specific physical exergy
bph is expressed as:
bph hph T0 s ph (2.4)
where hph,sph denote the specific physical enthalpy and entropy.

Physical exergy can be divided into a part depending on pressure and another
depending on temperature. The temperature-dependent part corresponds to the
variations of enthalpy andentropy at p0.
T
bphT ('hp0 T0 's p0 ) | (2.5a)
T0
In the case of ideal gases eqn (2.5a) takes the form
bphT ¦yh
i
i phi T0 ¦ yi 's pi
i
(2.5b)
Under the additional assumption of a constant thermal capacity the tempe-

rature-dependent part of the physical exergy becomes:
§ T·
bphT c p ¨ T T0 T0 ln ¸ (2.5c)
© T0 ¹
where cp denotes the specific thermal capacity at constant pressure.

The temperature-dependent part of the physical exergy is always positive and
equals zero at environmental temperature. Hence, below the environmental tempe-
rature it increases when the temperature of the considered substance decreases.
The pressure-dependent part increases with pressure and is negative when
the pressure is lower than the ambient one. As the temperature-dependent part is
computed at constant ambient pressure and temperature increasing from T0 to T, so
the pressure-dependent part corresponds to the isothermal variations of enthalpy
and entropy at T = const:
p
bphp ('h T0 's )T const | (2.6a)
p0
In the case of ideal gases the formula becomes:
p
bphp RT0 ln (2.6b)
p0
CALCULATION OF EXERGY 21
Figure 2.1: Reduced physical exergy of a perfect gas.
The pressure-dependent part of the physical exergy of a solid or liquid sub-

stance can usually be calculated under the assumption that its specific volume
v does not depend on the pressure:
bphp v( p p0 ) (2.6c)
Figure 2.1 presents the reduced dimensionless physical exergy of a perfect gas.
2.3. Chemical exergy

Chemical exergy expresses the exergy content of the substance at environmental
temperature and pressure [57]. Its value results from the difference of composi-
tion of this substance in relation to the commonly appearing components of the
environment. Some authors maintain that chemical exergy should be calculated
from the level of an equilibrium environment [105, 106]. Such an assumption
would facilitate the calculation of the chemical exergy, because the state of every
component of an equilibrium environment could be used as a reference level
for the calculation of the chemical exergy. It is, however, worth stressing that the
state of the natural environment is far from thermodynamic equilibrium, and the
attainment of such a dead state is impossible because of the continuous trans-
mission of the solar radiation representing not only a flow of energy but also a
flow of entropy. Some part of the transmitted energy is accumulated in the form
of the chemical energy of plants, the potential energy of liquid water, etc., but the
prevailing part is dissipated. The absorption of solar radiation connected with the
emission of infrared radiation of the Earth’s surface (characterized by a much

greater entropy) is irreversible, causes huge exergy losses (about 113u106
GW [88]) and generates components that are not in equilibrium with the
prevailing components of nature.
Ahrendts [1] calculated the equilibrium composition of the environment
at a given ambient temperature and pressure. He treated the natural environ-
ment as a closed system with a given temperature and pressure. He assumed
various values of the thickness of the external layer of the lithosphere (1m,
10m, 100m, 1000m), considered 17 chemical elements and 692 of their
compounds, and took into account the total mass of each element. Calcu-
lations of the equilibrium composition of the environment yielded values
very different from those measured in the field: the differences are extremely
large for the atmosphere (see table 2.1). In an equilibrium state, the oxygen
would be mainly combined in nitrates solved in seawater, and the con-
centration of free oxygen in the atmosphere would amount to some ppm
only.
In order to calculate the chemical exergy in a non-equilibrium environ-
ment, Szargut [57] introduced the concept of reference species. In chemical
reactions only the number of atoms (the amount of moles) of each individual
element does not change. Therefore, for every element taking part in a chem-
ical reaction a separate reference species containing the considered element
should be accepted. To prescribe the lowest (but appearing in nature) refer-
ence level of chemical exergy, the most common components of the natural
environment should be chosen as reference species [59, 70].
It should be stressed that the reference species of particular elements are
independent of each other. It is impossible to formulate a chemical reaction
comprising only reference species. Therefore, the problem of chemical equi-
librium between reference substances does not exist.
After selecting the reference species, a reference reaction can be for-
mulated for every chemical compound. In this reaction, except the considered
compound (or element), only reference substances appear: influent refeence
species supplementing the considered compound and effluent reference spe-
cies resulting from the reaction.
Table 2.1: Equilibrium composition of atmospheric air in a system with an external

layer of the lithosphere 100m thick T0=298 K, p0=77 kPa.
Component Molar fraction
N2 0.9451
H2O 0.0397
Ar 0.0117
CO2 0.0033
O2 2.6 ppm
Example 2.1. Formulation of the reference reaction.

The following reference species have been chosen: CO2 for carbon, O2 for
oxygen and CaCO3 for calcium. The reference reaction for the element Ca has the
following form:
Ca + ½ O2 + CO2 CaCO3
The reference species O2 and CO2 appear as the influent and CaCO3 as the effluent
reference species.
The ambient temperature and pressure are not constant. Usually changes of
these parameters influence, though slightly, the value of chemical exergy. The
chemical composition of the natural environment is also not the same in various
places. Calculations of the chemical exergy are usually difficult. In order to prepare
the tables of chemical exergy, the concept of standard chemical exergy has been
introduced [59]. It is calculated at normal temperature and pressure (25qC, 1 Atm)
and conventional standard concentration of the reference species in the environ-
ment. This standard concentration results from the mean composition of atmos-
pheric air, sea water and the external layer of the Earth’s crust.
The standard chemical exergy of a chemical compound or element can be
calculated by means of the exergy balance of a reversible standard reference reac-
tion. The reactants taking part in a standard chemical reaction appear sepa-
rately in standard state. The normal standard state denotes additionally a normal
temperature.
bchq ' r G q ¦ Bchk

q
¦ Bchj
q
(2.7)
k j
where ' r G q = normal standard free energy of the reference reaction

¦ B ,¦ B
k
q
chk
j
q
chj
= sum of the normal standard chemical exergies of the effluent and
influent reference species.
Example 2.2. Calculation of the standard chemical exergy of a chemical

element.
The normal standard free energy of the reference reaction cited in Example
2.1 is 'rGq= –738.6 kJ/mol CaCO3. The normal standard values of the chemical
exergy of the reference species are 16.3 kJ/mol CaCO3, 19.87 kJ/mol CO2 and
3.97 kJ/mol O2. According to eqn (2.7) the standard chemical exergy of the
element Ca is
bchq 738.6 16.3 19.87 1.5 u 3.97 729.1 kJ/mol
The formulation of the reference reaction and the application of eqn (2.7) are
required only for chemical elements. After calculating the normal standard chemical
exergy of the chemical elements, the normal chemical exergy of every chemical
compound can be calculated by means of the exergy balance of the reversible

normal standard reaction of formation of the considered compound
bchq ' f G q ¦ nel bchel

q
(2.8)
el
where bchq , bchel

q
= normal standard chemical exergy of the compound and element
nel = number of moles of the elements per unit of the compound
'fGq = Gibbs normal standard free energy of formation of the compound.
Example 2.3. Calculation of the standard chemical exergy of a chemical

compound.
Gibbs normal standard free energy of formation of the compound SO3 is 366.5
kJ/mol. The normal standard exergies of the elements are 609.6 kJ/mol S and 3.97
kJ/mol O2. According to eqn (2.8) the normal standard
bchq 366.5 609.6 1.5 u 3.97 249.1 kJ/mol.
For elements commonly occuring in atmospheric air, the main components

of air can be accepted as reference species (O2, N2, CO2, H2O, D2O, Ar, He, Ne, Kr,
Xe). The specific chemical exergy of gaseous reference species results from its
molar fraction in the air:
bchrs RrsT0 ln zrs 0 (2.9)
where Rrs,zrs0 designate the gas constant of the reference species and its molar
fraction in the environment (in the air when considering gaseous reference species).
For gaseous substances containing only gaseous reference species the for-
mulation of a reference reaction and the use of the tables of the standard
chemical exergy is not necessary. The calculation of the chemical exergy may
take into account only the change of the concentration of the components of the
considered substance:
yi
Bch nT0 R ¦ yi ln (2.10)
i y0 i
where n = amount of moles of the substance

yi, y0i = mol fraction of the ith component in the considered substance and in
the atmospheric air
R = universal gas constant.
When calculating the chemical exergy of liquid or gaseous water, it should
be taken into account that at ambient temperature the exergy of saturated vapour
does not depend on its quality.
When considering processes of humid air, the reference state for the
chemical exergy of liquid or gaseous water may be determined by means of the
local ambient parameters. For locations remote from the sea the concentration of
water vapour in the ambient air may determine the chemical exergy of water. In
this case, according to eqn (2.10), the chemical exergy of saturated liquid water
or vapour can be calculated by means of the relative humidity of atmospheric air:
1
bchc 0 bchcc0 RwT0 ln (2.11)
M0
where bchc 0 , bchcc0 = chemical exergy of saturated liquid and saturated vapour at
ambient temperature
Rw = gas constant of water
M0 = relative humidity of atmospheric air.
The chemical exergy of liquid water or water vapour should additionally in-
clude the work of the expansion of liquid water from the ambient pressure to the
pressure of saturated vapour at ambient temperature:
1
bchw v c ( p0 ps 0 ) RwT0 ln (2.12a)
M0
It is, however, not convenient to calculate separately the physical and chemical
exergy of liquid water or water vapour. The sum of these quantities can be ex-
pressed as follows:
1
bw h h0c T0 ( s s0c ) RwT0 ln (2.13)
M0
where h0c , s0cc = specific enthalpy and entropy of saturated liquid water at the
ambient temperature.
The values of saturated vapour at ambient temperature may be also introduced into
eqn (2.13).
In countries where fresh water is scarce, its production by desalination of
seawater may be necessary. In such a case the concentration of pure water in the
seawater may determine the reference level of the chemical exergy of water.
The following formula expressing the chemical exergy of pure water (equal to
the minimum desalination exergy) results from the assumption that pure water
contained in seawater may be treated as a component of an ideal solution. Taking
into account the molar fraction z of salt in seawater, we obtain
1
bchw v c ( p0 ps 0 ) RT0 ln (2.12b)
1 z
The first component of eqn (2.12b) may be neglected.

For other elements, solid reference species present in the external layer of the
Earth’s crust (products of weathering) and ionic (or molecular) reference species
present in the sea water have been proposed [38, 59, 64, 66]. Similarly to eqn (2.9),
the chemical exergy of solid or ionic reference species should depend on their
concentration in the environment. It would not be acceptable to assume a zero val-
ue for the chemical exergy of solid reference species because it would denote, that
they are commonly accessible in the environment and could be gained without any
consumption of work. The external layer of the Earth's crust is a very complicated
mixture of solid solutions. It is not possible to calculate exactly the concentration
exergy of solid reference species. Szargut [59] proposed to evaluate the con-
centration exergy of solid reference species by means of the formula (2.9) valid for
ideal solutions.
The conventional mean molar fraction of solid reference species in the
external layer of the Earth’s crust results from geochemical data [41] and from
the evaluated mean molecular mass M0 of the upper layer of the Earth’s crust
[59]:
l
zrs 0 n0i ci M 0 (2.14)
li
where noi = mean molar concentration of ith element in the continental part of the
Earth’s crust
li = number of the atoms of ith element in the molecule of the reference
species
ci = fraction of the element appearing in the form of reference species.
The value M0=135.5 kg/kmol results from the composition of a mean sample
of the lithosphere, calculated by Szargut [66] according to the geochemical data.
The values of ci have been assumed conventionally according to geochemical
information about the appearance of the assumed reference species. It is not
necessary to determine exactly the value zni because it appears under the logar-
ithm in eqn (2.9). Multiplication of zni by 100 changes the value resulting from
eqn (2.9) by only 10 kJ/mol. The values for the elements Cr, Ir, Pd, Sn and Ti
have been corrected according to the data of Taylor and McLennan [91, 92] and
calculation results of Ranz-Villarino et al [44]. The exergy values of Al and Mn
are corrected according to Rivero and Garfias [109].
Example 2.4. Calculation of the standard chemical exergy of a solid

reference species.
The mean molar concentration of the element Ca in the external layer of the
Earth’s crust is 1.03u10–3. The fraction of the element Ca appearing in the form
of the reference substance CaCO3 has been assumed as c=0.01. Hence, according
to eqn (2.14) the conventional mean molar fraction of the reference species in
the lithosphere is
zrs 0 1.03 u 103 u 0.01 u 135.5 1.4 u 103

According to eqn (2.9) the standard chemical exergy of the reference species is
bchq 8.3143 u 10 3 u 298 u ln0.0014 =16.3 kJ/mol
The assumption of solid reference species from among the compounds most
stable in normal conditions, is not always reasonable. Sometimes the formation of
most stable compounds is kinetically blocked and therefore they do not commonly
appear in the environment. For example the nitrates NaNO3, KNO3, Ca(NO3)2 are
most stable but do not commonly appear in the environment [1]. Therefore, the
negative value of the chemical exergy of the mentioned nitrates should be accepted.
The compounds of very rare elements should not be accepted as reference species
either because of a small likelihood of their formation. However, the chemical
exergy of commonly appearing components of the lithosphere should not have a
negative chemical exergy.
Components dissolved in sea water can be convenient as reference species
because their mean concentration in sea water is sufficiently well known for many
elements. However, only for dissolved molecules and for monocharged and bi-
charged ions the theory of thermodynamic functions is sufficiently exact. There-
fore, only such kind of reference species is to be accepted. Sometimes the use of
reference species dissolved in sea water results in negative values of the standard
chemical exergy of solid compounds which are relatively common on the Earth's
surface. Such unsatisfactory results have been obtained in the case of elements of
the second column in the periodic system and moreover for some compounds of F
and Mn. In such cases the assumption of solid reference species was unavoidable
[71].
The formula expressing the standard chemical exergy of elements with
reference species dissolved in seawater has been proposed by Morris [37, 38, 69]:
ª 1 º
bchq j « ' f Grq zbchq H2 ¦ vk bchk
q
RTn [2.303 z (pH) ln mn Ȗ]» (2.15)
¬ 2 k ¼
where j = number of reference ions or molecules derived from one molecule of

the element under consideration
' f Grq = normal standard free energy of formation of the reference species
z = number of elementary positive charges of the reference ion
Qk = number of molecules of additional elements present in the molecule of
the reference species
bchq H2 , bchq k = standard chemical exergy of hydrogen gas and of the kth additional
element,
mn = conventional standard molarity of the reference species in sea-
water,
J = activity coefficient (molarity scale) of the reference species in
seawater,
pH = 8.1; exponent of the concentration of hydrogen ions in seawater.
The activity coefficient of single ions can be calculated by means of the Debye-
Hückel equation:
Azi2 I
log Ȗ i (2.16)
1 ai B I
where A = 0.51 kg1/2 mol–1/2 for water at 25qC

B = 3.287u109 kg1/2 m–1 mol–1/2 for water at 25qC
ai = effective diameter of the ion
I = ionic strength of the electrolyte.
The ionic strength of the electrolyte results from the following equation:
1
I ¦ mi zi2
2 i
(2.17)
where mi = molarity of the ion, mol/kg H2O

zi = number of elementary electric charges on the ion.
The ion Cl– prevails among the negative ions in seawater, and therefore, the
data for chlorides can be assumed as activity coefficients of the positive ions Na+,
K+. The activity coefficients of the negative ions Cl– and SO--4 can be estimated in
reference to the predominant positive ion Na+.
The following ionic and molecular reference species dissolved in sea water
have been accepted:
AgCl , Bi(OH)3 aq, BiO , Br , CdCl2 aq, Cl , Cs , Cu , HAsO
4 , HPO 4 ,
HgCl4 , JO3 , K , Li , MoO

4 , Na , Ni

, PbCl2 aq, Rb ,SO
4 ,SeO 4 , WO 4 , Zn .
Example 2.5. Calculation of the standard chemical exergy with an ionic

reference species.
The reference ion of sulfur is SO 24 . Its normal standard free energy of
formation is –744.6 kJ/mol, and j = 1, z = –2. An additional element in the reference
ion is oxygen, nk = 2. The values of the standard chemical exergy are 236.09 kJ/mol
H2 and 3.97 kJ/mol O2. The conventional standard molarity of the reference ion
in seawater is m = 0.0117, and its activity coefficient is J = 0.11. According to eqn
(2.15) the standard chemical exergy of sulfur is
744.6 236.09 2 u 3.97 8.3143 u 103 u 298 u [2.303 u 2 u 8.1 ln(0.0117 u 0.11)]
609.6 kJ/mol
The calculated values of the standard exergy of elements are cited in table 2.2.
Table 2.3 contains unsatisfactory negative values obtained by means of the ionic
reference species for some compounds of the elements of the second column in
the periodic system. The value of the normal chemical exergy of Au calculated
by means of ionic reference species is surprisingly small. On the other hand,
the value for graphite obtained by means of the ionic reference species differs
only slightly from that resulting from the gaseous reference species
Table 2.2: Standard chemical exergies of the elements.
Chemical element Reference species Chemical element
Order Chem Concentration Chemical state c, J U, m, x Standard Free State Standard
no symbol in Earth’s formula chem. exergy of chem.
crust exergy formation exergy
nch bchq ' f Gq bchq
kmol/kg
kJ kJ/mol kJ/mol
1 2 3 4 5 6 7 8 9 10 11
1 Ag 3.7u10–10 AgCl2– aq J=0.6 m=2.7u10–9 – –215.5 s 70.2
2 Al 3.05u10–3 AlSiO5 s c=0.01 x=2.1u10–3 15.3 –2 441.0 s 795.7
3 Ar – Ar g – p=0.906 11.69 0 g 11.69
4 As 2.4u10–8 HasO42– aq J=0.1 m=2.1u10–8 – –714.7 s 494.6
5 Au 2u10–11 Au s c=0.5 x=1.4u10–9 50.5 0 s 50.5
6 B 9.3u10–7 B(OH)3 aq J=1.0 m=3.4u10–4 – –968.8 s 628.5
7 Ba 3.1u10–6 BaSO4 s c=0.01 x=4.2u10–6 30.7 –1 361.9 s 775.1
8 Be 3.1u10–7 Be2SiO4 s c=0.01 x=2.1u10–7 38.1 –2 033.3 s 604.4
9 Bi 8.1u10–10 BiO+ aq J=0.6 m=1u10–10 – –146.4 s 274.5
10 Br 3.1u10–8 Br– aq J=0.68 m=8.7u10–4 – –104.0 Br2l 101.2
11 C 1.7u10–5 CO2 g – p=0.0335 19.87 –394.36 s,gr 410.26
12 Ca 1.03u10–3 CaCO3 calcite s c=0.01 x=1.4u10–5 16.3 –1 129.0 s 729.1
13 Cd 1.8u10–9 CdCl2 aq J=1.0 m=6.9u10–11 – –359.4 s 293.8
14 Ce 4.3u10–7 CeO2 s c=0.02 x=1.2u10–6 33.8 –1 024.8 s,J 1054.6
15 Cl 3.7u10–6 Cl– aq J=0.68 m=0.5657 – –131.26 Cl2g 123.6
16 Co 3.5u10–7 CoFe2O4 s c=0.002 x=9.5u10–8 40.1 –1 032.6 s,III 312.0
17 Cr 1.5u10–6 K2Cr2O7 s c=0.0l x=1u10–6 34.3 –1 882.3 s 584.7
18 Cs 2.2u10–5 Cs+ aq J=0.6 m=2.3u10–9 – –282.2 s 404.4
19 Cu 8.7u10–7 Cu2+ aq J=0.2 m=7.3u10–10 – +65.5 s 134.2
20 D – D2O g – p=3.42u10–4 31.2 –234.55 D2g 263.8
Table 2.2: Standard chemical exergies of the elements (continued)
kmol/kg
kJ kJ/mol kJ/mol
1 2 3 4 5 6 7 8 9 10 11
21 Dy 1.8u10–8 Dy(OH)3 s c=0.02 x=4.9u10–8 41.7 –1 294.3 s,D 975.9
22 Er 1.7u10–8 Er(OH)3 s c=0.02 x=4.6u10–8 41.9 –1 291.0 s 972.8
23 Eu 7.9u10–9 Eu(OH)3 s c=0.02 x=2.lu10–8 43.8 –1 320.1 s 1003.8
24 F 3.3u10–5 CaF2.3Ca3(PO4)2 s c=0.01 x=2.2u10–5 26.6 –12 985.3 F2g 504.9
25 Fe 1.0u10–3 Fe2O3 s c=0.1 x=6.8u10–3 12.4 –742.2 s,D 374.3
26 Ga 2.2u10–7 Ga2O3 s c=0.02 x=3.0u10–7 37.2 –998.6 s 514.9
27 Gd 3.4u10–8 Gd(OH)3 s c=0.02 x=9.2u10–9 40.2 –1 288.9 s,D 969.0
28 Ge 1.4u10–8 GeO2 s c=0.05 x=9.5u10–8 40.1 –521.5 s 557.6
29 H – H2O g – p=2.2 9.49 –228.59 H2g 236.09
30 He – He g – p=4.85u10–4 30.37 0 g 30.37
31 Hf 1.7u10–8 HfO2 s c=0.05 x=1.2u10–7 39.5 –1 027.4 s,D 1062.9
32 Hg 4.0u10–10 HgCl42– aq J=0.1 m=3.4u10–10 – –446.9 1 115.9
33 Ho 7.2u10–9 Ho(OH)3 s c=0.02 x=1.0u10–8 43.9 –1 294.8 s,D 978.6
34 I 3.9u10–9 IO3– aq J=0.6 m=5.2u10–7 – –128.0 I2s 174.7
35 In 8.7u10–10 In2O3 s c=0.05 x=2.9 u10–9 48.7 –830.9 s 436.8
36 Ir 1.04u10–13 IrO2 s c=0.005 x=3.6u10–12 75.1 –185.6 s 256.7
37 K 5.4u10–4 K+ aq J=0.64 m=1.04u10–2 – –282.44 s 366.6
38 Kr – Kr g – p=9.7u10 34.36 0 g 34.36
39 La 2.2u10–7 La(OH)3 s c=0.02 x=6.0u10–7 35.5 –1 319.2 s,D 994.6
kmol/kg
kJ kJ/mol kJ/mol
1 2 3 4 5 6 7 8 9 10 11
40 Li 2.9u10–6 Li+ aq J=0.68 m=2.5u10–5 – –294.0 s 393.0
41 Lu 2.9u10–9 Lu(OH)3 s c=0.02 x=7.9u10–9 46.2 –1 259.6 s 945.7
42 Mg 9.6u10–4 Mg3SiO10(OH)2 s c=0.06 x=2.6u10–3 14.8 –5 543.0 s 626.1
43 Mn 1.7u10–5 MnO2 s c=0.01 x=2.3u10–5 26.5 –465.2 s 487.7
44 Mo 1.6u10–8 MoO42– aq J=0.1 m=1.1u10–7 – –836.4 s 730.3
45 N – N2 g – p=75.78 0.72 0 N2g 0.72
46 Na 1.03u10–3 Na+ aq J=0.68 m=0.474 – –262.05 s 336.6
47 Nb 2.2u10–7 Nb2O3 s c=0.0l x=1.5u10–7 39.0 –1 766.4 s 899.7
48 Nd 1.9u10–7 Nd(OH)3 s c=0.02 x=5.1u10–7 35.9 –1 294.3 s,D 970.1
49 Ne – Ne g – p=1.77u10–3 27.19 0 g 27.19
50 N1 1.3u10–6 Ni2+ aq J=0.2 m=1.2u10–7 – –45.6 s 232.7
51 C – O2 g – p=20.39 3.97 0 O2g 3.97
52 Os 5.0u10–13 OsO4 s c=0.005 x=3.4u10–13 71.62 –305.1 s 368.1
53 P 3.4u10–5 HPO42– aq J=0.1 m=4.9u10–7 – –1 089.3 s,w 861.4
54 Pb 7.7u10–8 PbCl2 aq J=1.0 m=4.2u10–11 – –297.2 s 232.8
55 Pd 4.7u10–12 PdO s c=0.005 x=3.2u10–12 65.6 –82.5 s 146.1
56 Pr 5.8u10–8 Pr((OH)3 s c=0.02 x=1.6u10–7 38.8 –1 285.1 s,D 963.8
57 Pt 2.6u10–11 PtO2 s c=0.005 x=1.8u10–11 61.3 –83.7 s 141.0
58 Pu 6.2u10–20 PuO2 s c=0.01 x=8.4u10–20 108.9 –995.1 s 1100.0
kmol/kg
kJ kJ/mol kJ/mol
1 2 3 4 5 6 7 8 9 10 11
59 Ra 4.4u10–15 RaSO4 s c=0.05 x=3.0u10–14 77.2 –1 364.2 s 823.9
60 Rb 1.05u10–6 Rb+ aq J=0.6 m=1.4u10–6 – –282.4 s 388.6
61 Re 5.4u10–12 Re2O7 s c=0.01 x=3.6u10–12 65.3 –1 067.6 s 559.5
62 Rh 9.7u10–12 Rh2O3 s c=0.005 x=3.3u10–12 65.5 –299.8 s 179.7
63 Ru 1.0u10–12 RuO2 s c=0.005 x=6.08u10–13 69.5 –253.1 s 318.6
64 S 8.1u10–6 SO42– aq J=0.11 m=1.17u10–2 – –744.6 s,rh 609.6
65 Sb 1.6u10–9 Sb2O5 s c=0.001 x=1.1u10–10 56.8 –829.3 s,III 438.1
66 Sc 1.1u10–7 Sc2O3 s c=0.05 x=3.7u10–7 36.7 –1 819.7 s,D 925.2
67 Se 6.3u10–10 SeO42– aq J=0.1 m=1.2u10–9 – –441.4 s 346.5
68 Si 1.0u10–2 SiO2 D quartz s c=0.3 x=0.407 2.2 –856.7 s 854.9
69 Sm 4.0u10–8 Sm(OH)3 s c=0.02 x=l.lu10–7 39.7 –1 314.0 s,D 993.6
70 Sn 1.7u10–8 SnO2 s c=0.2 x=4.6u10–7 36.2 –519.6 s,w 551.9
71 Sr 4.3u10–6 SrCO3 II s c=0.05 x=2.9u10–5 25.9 –1 140.1 s 749.8
72 Ta 1.1u10–8 Ta2O5 s c=0.0l x=7.5u10–9 46.4 –1 911.6 s 974.0
73 Tb 6.3u10–9 Tb(OH)3 s c=0.02 x=1.7u10–8 44.9 –1 314.2 s,D 998.4
74 Te 1.4u10–11 TeO2 s c=0.005 x=9.5u10–12 62.9 –270.3 s 329.2
75 Th 4.0u10–8 ThO2 s c=0.05 x=2.7u10–7 37.5 –1 169.1 s,D 1202.6
76 Ti 5.9u10–5 TiO2 s c=0.02 x=1.6u10–4 21.7 –889.5 s,II 907.2
77 Tl 2.2u10–9 T12O4 s c=0.01 x=1.5u10–9 60.4 –374.3 s,D 194.9
kmol/kg
kJ kJ/mol kJ/mol
s1 2 3 4 5 6 7 8 9 10 11
78 Tm 2.8u10–9 Tm(OH)3 s c=0.02 x=7.6u10–9 46.3 –1 265.5 s 951.7
79 U 1.1u10–8 UO3.H2O s c=0.01 x=1.5u10–8 44.7 –1 395.9 s,III 1196.6
80 V 2.7u10–6 V2O5 s c=0.02 x=3.7u10–6 31.0 –1 419.6 s 720.4
81 W 8.2u10–9 WO42– s J=0.1 m=5.6u10–10 – –920.5 s 827.5
82 Xe – Xe g – p=8.7u10–6 40.33 0 g 40.33
83 Y 3.7u10–7 Y(OH)3 s c=0.02 X=1.0u10–6 34.2 –1 291.4 s,D 965.5
84 Yb 1.7u10–8 Yb(OH)3 s c=0.02 x=4.6u10–8 41.9 –1 262.5 s,D 944.3
85 Zn 1.1u10–6 Zn2+ aq J=0.2 m=1.7u10–8 – –147.3 s 339.2
86 Zr 1.8u10–6 ZrSiO4 s c=0.1 x=2.4u10–5 26.4 –1 919.5 s,D 1083.4
2.4. Enthalpy of devaluation

In order to facilitate a comparison of the energy and exergy balance, the concept
of enthalpy of devaluation has been introduced by Szargut [57, 59]. It expresses
the chemical energy of a chemical compound calculated from the level of con-
ventional reference substances commonly appearing in the environment. For
many chemical elements, the same reference substances have been assumed as
for the chemical exergy. The enthalpy of devaluation is a part of the enthalpy of
a material stream. The values of the normal enthalpy of devaluation of pure
chemical compounds are reported in table I at the end of this book (together with
the values of the normal chemical exergy). In contrast to the chemical exergy,
the enthalpy of devaluation of reference substances is always zero. Hence, the
assumed reference species for the enthalpy of devaluation can be easily found in
table I. For example, CaCO3 is the reference species of Ca; CaSO42H2O
(gypsum) is the reference species of S; CaCO3MgCO3 represents the reference
species of Mg; and Ca3PO4 the reference species of P. Similarly NaCl is the
reference species of Cl, and Na2SO4 is the reference species of Na.
Table 2.3. Standard chemical exergies of solid substances, resulting from the
data of reference species dissolved in seawater.
Free energy Normal

of formation chemical
Chemical Reference species of the ' f G q kJ exergy bchq
formula elements mol–1 kJ mol–1
1 2 3 4
Au AuCl2–, Cl– 0 15.4
C HCO3–, O2 g 0 404.5
CaCO3 (calcite) Ca2+, CO2 g, O2 g –1 129.0 –0.4
2+ 2+
CaCO3.MgCO3 Ca , Mg , CO2 g, O2 g –2 163.6 –7.8
2+
CaCO3 s, Mg , CO2 g, O2 g –2 163.6 8.9
CaF2.3Ca3(PO4)2 Ca2+, F–, HPO42–, O2 g –12 985.3 –199.0
CaCO3 s, F–, HPO42–, O2 g –12 985.3 –32.0
Ca2(PO4)2 Ca2+, HPO42–, O2 g –3 885.3 –9.4
CoFe2O4 Co2+, Fe2O3 s, O2 g –1 032.6 –27.5
2+
Co3O4 Co , O2 g –772.8 –19.1
Mg3Si4O10(OH)2 Mg2+, SiO2 s, O2 g, H2O g –5 543.0 –30.5
(talc)
MnO2 Mn2+, O2 g –465.2 –39.2
The enthalpy of devaluation of the compounds of C,H,O and N equals their

lower heating value. The enthalpy of devaluation of the compounds of C,H,O,N
and S is slightly higher than the heating value because the enthalpy of
devaluation of S (725.42 MJ/kmol) is higher than its heating value (296.83
MJ/kmol).
2.5. Chemical exergy of organic fuels
The chemical exergy of gaseous and liquid organic fuels can be determined by
means of the tables of the standard chemical exergy or, according to Fan and
Shieh [17], by means of the group contribution method (if the chemical for-
mulae of their components are known). This is, however, not possible in the
case of the majority of solid and liquid organic fuels consisting of complex
solutions and mixtures of many (usually unknown) compounds. An exact cal-
culation of the chemical exergy is not possible in this case. An approximate
calculation method proposed by Styrylska and Szargut [58] is based on an
analogy with the chemical exergy of pure organic substances. After calculating
the chemical exergy of several organic substances, approximate formulae have
been derived expressing the ratio E of their chemical exergy to the lower
heating value as a function of the atomic ratio of the elements C, H, O, N, S.
The most important formulae are:
— For solid C,H,O,N compounds
H O N O
ȕ 1.0347 0.0140 0.0968 0.0493 ; 0.5 (2.18a)
C C C C
1.044 0.016(H/C) 0.3493(O/C)[1 0.0531(H/C)] 0.0493(N/C) O

ȕ ; 2 (2.19a)
1 0.4124(O/C) C
— For liquid C,H,O,S compounds
H O S§ H· O
ȕ 1.047 0.0154 0.0562 0.5904 ¨1 0.175 ¸ ; 1 (2.20a)
C C C© C¹ C
For technical fuels it is more convenient to introduce the mass fractions

into eqns (2.18a), (2.19a) and (2.20a).
— For bituminous coal, lignite, coke and peat, it results from eqn (2.18a):
zH 2 zO2 z N2
ȕ 1.0437 0.1896 0.2499 0.0428 (2.18b)
zC zC zC
— For wood, from eqn (2.19a):
zH 2 zO 2 ª zH º zN2
1.0412 0.2160 0.2499 «1 0.7884 2 » 0.0450 z
zC zC ¬ zC ¼ C
ȕ (2.19b)
zO2
1 0.3035
zC
— For liquid technical fuels, from eqn (2.20a):
zH 2 zO2 zS § zH ·
ȕ 1.041 0.1728 0.0432 0.2169 1 2.0628 2 ¸ (2.20b)
zC zC zC ¨© zC ¹
The values resulting from eqns (2.18a)–(2.20a) can be applied only to the
combustible portion of the technical fuel. The lower heating value of the com-
bustible substance of a moist technical fuel results from the formula:
H Lc H L Lzw (2.21)
where HL = lower heating value of moist technical fuel

L = enthalpy of water vaporization
zw = mass fraction of water in moist fuel.
Equations (2.18a) and (2.19a) have been determined without taking into
account the sulfur content, because of the lack of sufficient thermo-chemical
data. The chemical exergy of solid fuels containing sulfur can be approximately
calculated under the additional assumption that sulfur appears as a free element:
bch ( H L Lzw )ȕ (bchS H S ) zS bcha za bchw z w (2.22)
where zS, za = mass fraction of sulfur and ash

bch S, bch a, bch w = standard chemical exergy of sulfur, ash and liquid water.
For liquid fuels, the calculation proceeds as follows:
bch ( H L Lzw )ȕ bchw z w (2.23)
In cases in which an approximate value suffices, the values from table 2.4 can be
used.
The standard chemical exergy of pure organic substances can be calculated by
means of the group contribution method. Per 1 mol of the considered substance:
bchq ¦gb
i
i gi (2.24)
Table 2.4. Ratio of the standard chemical exergy of organic fuels to the lower
and higher heating value.
Fuel bch /HL bch /HH
Hard coal 1.09 1.03

Lignite 1.17 1.04
Coke 1.06 1.04
Wood 1.15 1.05
Liquid HC-fuels 1.07 0.99
Natural gas (high CH4) 1.04 0.94
Coke-oven gas 1.00 0.85
Blast-furnace gas 0.98 0.97
where gi = number of ith groups in the molecule under consideration

bgi = contribution of the ith group to the standard chemical exergy of the
compound.
The values of bg i are reported in table II at the end of the book.
Example 2.6. Calculation of the standard chemical exergy by means of the
group contribution method.
The molecule of liquid methyl-alcohol contains one CH3 group (with bg =
651.46 kJ/mol) and one OH group with bg = –33.97 kJ/mol). The standard chemical
exergy of liquid methyl-alcohol is
bchq 752.03 33.97 718.06 kJ/mol
According to [69] the exact value is 718.0 kJ/mol.
2.6. Chemical exergy of solutions
The chemical exergy of solutions can be calculated by means of the partial specific
exergies of the solutes:
Bch ¦n b
i
i chi (2.25a)
where ni = number of moles of the ith component

bchi = partial molar chemical exergy of the component.
The partial molar chemical exergy can be expressed in terms of the activity ai
of the component:
bchi bchi RT0 ln ai (2.26)

In the case of ideal solutions, the activity equals the molar fraction, and the specific
chemical exergy per 1 mole of solution may be expressed as follows:
bch ¦ yb
i
i chi RT0 ¦ yi ln yi
i
(2.25b)
The last term expresses the exergy loss due to mixing.

Table III at the end of the book contains the values of the standard chemical
exergy of species dissolved in an ideal aqueous solution (molarity 1 mol/kg H2O).
2.7. Exergy of thermal radiation

The exergy of the Earth’s infrared radiation, calculated with the assumption that the
Earth's surface is black, amounts to zero, and represents the reference level for the
calculation of the exergy of thermal radiation.
The exergy flux of the black surface emission per unit of the absorbing surface,
results from eqns (1.23) and (1.24), and from the scheme of the reversible prime
mover presented in fig. 2.2. The absorbing surface of the prime mover, parallel to
the black emitting surface has the area of 1m2. The prime mover absorbs the energy
flux ơb and emits the energy flux ơb0 the “waste” radiation of a black surface with the
environmental temperature T0. The energy balance of the prime mover is closed by
the stream of zero-exergy heat q0 delivered from the environment. The work
performed by the prime mover expresses the exergy flux of the black surface
radiation:
bb eb q0 eb 0 (2.27)
From the condition of reversibility of the considered prime mover and from eqn
(1.24) it results:
q 4 eb q0 4 eb 0
sb sb 0 or (2.28)
T0 3 T T0 3 T0
Figure 2.2: Reversible prime mover fed by a black radiation.

From eqns (2.27) and (2.28) it results:
bb
4
4 T0 1 § T0 ·
1 (2.29)
eb 3 T 3 ¨© T ¸¹
The same result was obtained by Petela [40] with a different method. eqn (2.29)
does not depend on the emissivity of the environment. Equation (2.29) may be
also applied to gray surfaces if their emissivity does not depend on the
wavelength.
When considering the exergy of the total radiation flux, not only the emi-
ssion but also the reflected radiation should be taken into account. In exact
calculations, the distribution of the radiation brightness over the wavelength
should be known. Usually, the actual radiation flux may be replaced by the
emission of a black surface. The equivalent temperature of this black surface can
be calculated from the condition of the equality of the energy fluxes.
The spectral distribution of solar radiation on the Earth’s surface depends on
the composition of the atmosphere and the path length through the atmosphere
determined by the position of the Sun.
Example 2.7. Exergy of the solar radiation.
Assuming the mean temperature of the Earth’s surface as 300K we obtain
from eqn (2.29) the ratio of exergy to energy of solar radiation above the
atmosphere: 0.9311. A more exact value, taking into account the spectral
distribution of solar radiation above the atmosphere, is 0.9327 [40]. At the
Earth’s surface the discussed ratio depends on the ambient terrestrial
temperature, on the position of the Sun and on the composition of the
atmosphere. At T0=289 K we obtain from eqn (2.29) the ratio 0.9336. Hence, the
exergy flow of solar radiation immediately absorbed by the Earth’s surface
amounts to 73,100 TW.
Example 2.8. Exergy balance of the Earth’s surface and atmosphere.
Figure 2.3 presents the exergy flows appearing above the Earth’s surface
and connected with the absorption of solar radiation and the emission of infrared
radiation [88]. The mean exergy flow of solar radiation reaching the external
layers of the atmosphere amounts to 162,400 TW. The reflection of solar
radiation from the upper layers of the atmosphere (48,700 TW) does not evoke
any exergy losses. Some part of the solar exergy is being destructed in the
atmosphere (32,400 TW) due to the absorption of solar radiation and re-emission
of infrared radiation. This exergy loss has not been classified to the NLUE
because the considered phenomenon occurs outside the zone of human existence.
The exergy flow of solar radiation heating the continents and oceans amounts to
43,200 TW. A prevailing part of this radiation is transformed into infrared
radiation of the Earth’s surface, partially transmitted to the cosmic space and
partially absorbed by the atmosphere and re-emitted to the Earth’s surface,
causing the greenhouse effect. Only a small part of the radiation heating the
Earth’s surface (about 370 TW [27]) is transformed into mechanical exergy of
Figure 2.3: Distribution of exergy flows above the Earth’s surface.
the wind, waves and sea-currents. Some part causes a weathering of rocks,
producing components necessary for the vegetation of plants [52].
The exergy flow used for evaporation is about 38,100 TW. A small part of this
exergy is transformed into the potential exergy of water droplets or ice particles
contained in clouds. The mass of evaporated water (assuming a mean temperature
of 25qC) amounts to 15u109 kg/s. Assuming the mean height of clouds as 2000m,
the potential exergy power of the clouds is 300 TW. A prevailing part of this exergy
is destroyed by rain- and snowfalls. Only a very small part (5 TW) is transformed
into the potential exergy of rivers and lakes [27]. The rivers and lakes are also a
renewable source of fresh water, necessary for human life (see point 6.6.2).
The radiation absorbed by the vegetation of plants (only the active part) has an
energy about 40 TW [27], (exergy about 37 TW). Only a small part of it is
transformed into the chemical exergy of plants (about 2.5 TW of energy and 2.9
TW of exergy). About 1 TW of the chemical exergy of plants is consumed by
humans.
The left part of fig. 2.3 represents exergy losses resulting from the radiation
exchange between the Earth and cosmic space. This space emits the long-wave
relict radiation. Its spectral composition represents a very low temperature

2.73K, and reaches the Earth continuously from all directions. It is worth
remembering that at a temperature lower than the ambient one the flow direc-
tions of energy and exergy are opposite to each other. Therefore, the infrared
emission of the Earth (whose exergy equals zero) causes an inflow of exergy,
which may be interpreted as exergy flow of the relict radiation of the space. The
positive exergy of this cold radiation results from the possibility to build a prime
mover using the ambient thermal radiation as a hot source and the cold radiation
as a cold sink of heat.
The exergy flow of the cold relict radiation is not small. Its energy flow is very
small, and amounts to 3.15u10–6 W/m2. However, the ratio of exergy to energy is
very high. From eqn (2.29) at T0 = 289 K it results that:
br
41.9 u 106 , br 147 W/m 2
er
The total flow of exergy of relict radiation reaching the Earth’s surface results from
the area of the Earth’s surface. Introducing the main radius of the Earth we obtain:
B r 4S u 63674402 u 147 74900 TW
The exergy flow of the relict radiation is 1.02 times larger than the exergy flow of
solar radiation absorbed by the Earth’s surface. The exergy of the relict radiation
does not produce any lasting energy effect on the Earth’s surface. Only the tempe-
rature of the upper layers of the atmosphere drops. The secondary radiation of these
layers also has a positive exergy (about 5200 TW) generated thanks to the des-
truction of the exergy of relict radiation. Only a small part of the exergy flow of the
mentioned kinds of cold radiation is absorbed by the Earth's surface. A prevailing
part is destroyed outside the zone of human existence. From the balance of natural
losses of utilizable exergy it results that only 7% of the considered losses (5400
TW) are due to the destruction of exergy of the relict radiation and cold radiation
of the upper layers of the atmosphere.
The exergy flows of solar radiation have also been analyzed by Wall and Gong
[106], but the exergy inflow resulting from cold space radiation has not been taken
into account.
2.8. Nuclear exergy

The energy of nuclear fuels is of very high quality because it intrinsically cor-
responds to a very high temperature. Hence, it can be assumed that the exergy of
nuclear raw materials equals the available energy. It can be determined from the
concentration of fissionable and fertile components in the raw material and from
the energy of fission.
The exergy efficiency of thermal nuclear power plants should take into
account only the exergy of fission of fissionable elements. The mean exergy of
fission per nucleus of 235U, 233U and 239Pu amounts to about 200MeV. Therefore,
the specific exergy (per kg) of the fissionable element can be expressed as
follows:
b=19.3  1012 1
M
qV (2.30)
where M is the molecular mass of the fissionable isotope.

Natural uranium contains 0.72% of fissionable 235U. The nuclear exergy of
natural uranium resulting from eqn (2.30) amounts to 584 000 MJ/kg (whereas
its chemical exergy is only 5 MJ/kg).
2.9. Exergy losses in thermal plants

2.9.1. Compressor
An isothermal compression of a perfect gas does not change its enthalpy nor its
internal energy. The amount of driving energy equals the amount of heat rejected
to the environment. Hence, the energy efficiency of an isothermal compressor is
equal to zero. The energy analysis cannot characterize the thermodynamic imper-
fection of a compressor cooled during the compression of the fluid. Only an exergy
analysis can correctly represent the useful effect of the compression.
The compression of a gas or vapour can be realized to increase the pressure
according to a specified design value, to overcome the flow resistance or to increase
the temperature (for example in a gas turbine cycle). In the first two casesonly the
isothermal increase of exergy represents the useful effect of the process. When
analyzing the compression of a perfect gas, the following formula expresses the
exergy efficiency of the compressor:
nRT
& 0 ln p2 p1
ηBT  (2.31)
| W& D |
where n& = molar flow rate of the compressed fluid

p1, p2 = initial and final pressure of the fluid
| W& D | = driving mechanical power.
Thus, the exergy component of the compressed fluid resulting from its increased
temperature, represents the external exergy loss of the system.
In the third case, the exergy efficiency should take into account also the tempe-
rature increase after the compression. For a perfect gas:
n&[c p (T2 − T0 − T0 ln T2 T0 )  RT0 ln p2 p1 ]

ηB  (2.32)
| W& D |
Example 2.9. Exergy balance of a two-stage piston compressor of air with an

interstage and cylinder cooling.
The following parameters result from thermal measurements:
ambient air: p0 = 0.1 MPa, T0 = 291 K, relative humidity M0 = 78%,

air before the first stage: p1 = 99 kPa, T1 = 291 K, V1 = 0.92 m3/s,
air after the first stage: p2 = 0.27 MPa, T2 = 368 K,
air before the second stage: p3 = 0.265 MPa, T3 = 300 K, M3 = 100%,
air after the second stage: p4 = 0.82 MPa, T4 = 393 K,
cooling water in the first stage: G I = 2.15 kg/s, TI = 292 K, TII = 296 K,
cooling water in the interstage cooler: G = 1.06 kg/s, TIII = 292 K, TIV = 308 K,
c
cooling water in the second stage: G II = 2.06 kg/s, TV = 292 K, TVI = 297 K,
driving electric power | N el | = 330 kW,
heat losses of the compressor cylinders immediately to the environment amount
to 8% of the heat transferred to the cooling water,
efficiency of the electric motor KM= 0.92.
The assumption has been made that after the interstage cooler the
compressed air does not contain any droplets of liquid water. The condensate of
air humidity flowing out of the interstage cooler has a temperature equal to that
of the cooled air.
Exergy loss in the electric motor:
G B M (1 KM ) N el 26.4 kW 26.4 kW.
Mechanical exergy loss in the compressor:
G B m KM N el Wi
where the internal driving power of the compressor | Wi | results from the energy
balance of both cylinders:
| Wi | H 2 H 1 H 4 H 3 1.08('H wI 'H wII )
where 'H wI , 'H wII = enthalpy increase of the cooling water stream in the first and
second stage.
The flow rate of humid compressed air is 0.03753 kmol/s.
The exergy efficiency of the compressor set should be calculated according
to eqn (2.31). The internal exergy losses result from the exergy balances of
particular links of the considered system. The external exergy loss comprises the
physical exergy of warm cooling water, the exergy of condensate formed in the
interstage cooler, and a component of exergy of the compressed air resulting
from its elevated temperature (only the increase of pressure is the aim of
compression in the con-sidered case). The relative exergy losses are related to
the driving electric power:
exergy efficiency of the system 57.90%

exergy loss in the electrical motor 8.00%
mechanical exergy loss in the compressor 9.55%
internal exergy loss in the first stage 6.76%
internal exergy loss in the interstage cooler 2.76%
internal exergy loss in the second stage 8.97%
external exergy losses 6.06%.
2.9.2. Steam or water boiler

The energy efficiency of a steam or water boiler expresses the ratio of the enthalpy
increase of the heated fluid to the chemical energy of fuel. Its value is high, and
amounts to 70–95%. However, the quality of chemical energy is much higher than
that of the physical energy of the produced hot fluid. Therefore, the exergy
efficiency of a boiler is much lower than the energy efficiency. This difference
results from two main causes:
(1) the combustion process is irreversible (see section 1.3.5.),
(2) the irreversible heat transfer between the combustion gases and the
heated fluid causes large exergy losses.
The exergy efficiency of the steam or water boiler can be expressed as follows:
G [h2 h1 T0 ( s2 s2 )] G (h2 h1 )(1 T0 Tm ) KE § T0 ·

KB ¨©1 T ¸¹ (2.33)
B F D E ch D m
The flow diagram of the considered exergy balance is presented in fig. 2.4.
Figure 2.4: Exergy balance of a two-stage air compressor.

where D = ratio of the chemical exergy of fuel to its chemical energy

KE = energy efficiency of the boiler
Tm = mean thermodynamic temperature of the heated fluid during heat
absorption
h2 h1
Tm (2.34)
s2 s1
In Europe, the lower heating value of fuel is used to determine the energy
efficiency of a boiler. In this case, the ratio D in eqn (2.33) should be related to
the lower heating value.
Exergy losses in a combustion process can be lowered by increasing the
combustion temperature. However, simultaneously the exergy loss increases due to
the irreversible heat transfer between the combustion gases and the heated fluid.
Therefore, the combustion air is preheated only to increase the energy efficiency
of the boiler by lowering the outlet temperature of the combustion gases. An
improvement of the exergy efficiency of the boiler can be attained by increasing the
mean thermodynamic temperature of the heated fluid. This method is applied in
steam power plants (increasing the temperature of live steam, secondary super-
heating). In water boilers for district heating systems, an increase of the mean
temperature of the heated water would not be expedient, because it would increase
the exergy losses in all subsequent heat transfer processes downstream.
The exergy efficiency of steam boilers usually amounts to 35–50%, and that
of water boilers to 15–25%.
Example 2.10. Exergy balance of a fluidized-bed steam boiler.

A fluidized-bed steam boiler fed with hard coal is schematically presented in
fig. 2.5. The combustion air is preheated by means of bleed steam taken from the
steam turbine. The combustion air preheaters and their fans are located outside
the system boundary. Therefore, limestone is delivered to the boiler to absorb the
sulfur oxides formed in the combustion room. The measurement data
determining the energy and exergy balance of the boiler are as follows:
ambient air: p0 = 0.0994 MPa, T0 = 298 K, relative humidity M0 = 60%,
primary combustion air: nap = 2.137 kmol/s, pap = 0.1178 MPa, Tap = 312 K,
secondary combustion air: nas = 0.831 kmol/s, pas = 0.1085 MPa, Tap = 302 K,
steam: G = 72.91 kg/s, pst = 13.72 MPa, Tst = 811.5 K,
st
feed water: Tfw = 490.3 K, pfw = 14.89 MPa,

fuel: lower heating value Hl = 19 106 kJ/kg, chemical composition: c = 0.5019,
h = 0.035, s = 0.0139, o = 0.0950, n = 0.0072, w = 0.229, a (ash) = 0.118,
ash from the boiler: total amount per fuel unit at = 0.1933 kg/kg
flying ash: fraction in the total ash gfa = 0.88, content of combustibles cfa =
0.0087,
content of CaO gCaO fa = 0.2209,
Figure 2.5: Scheme of a fluidized-bed steam boiler fed with hard coal.
bottom ash: fraction in the total ash gba = 0.12, content of combustibles cba =
0.0087, content of CaO gCaO ba = 0.4520, temperature Tba = 1107.8 K,
limestone: flow rate G ls = 0.795 kg/s,
combustion gases: temperature Tcg = 400.5 K, oxygen molar content (related to
dry gas) [O2] = 0.0539
immediate heat loss: H = 0.0061 (related to the chemical energy of fuel),
fan of fluidization air: driving power E el = 260 kW, electro-mechanical
efficiency Kme = 0.92.
The energy and exergy balance of the considered boiler is presented in fig.
2.6. The energy efficiency of the boiler is very high (93.6%), however, the
exergy efficiency is considerably smaller; it amounts to 43.3%. The internal
irreversible phenomena do not influence the energy balance of the boiler, they
influence considerably, however, the exergy balance. The relative internal exergy
loss taking into account the irreversibility of combustion and heat transfer
between the combustion gases and water, and the immediate heat loss to the
environment, amounts to 52.7%. The external energy- and exergy loss with
combustion gases is relatively small. The external exergy loss of combustion
gases also takes into account the chemical exergy resulting from the difference of
the chemical composition of the combustion gases and ambient air, and depends
mainly on the heightened concentration of CO2.
2.9.3. Thermal power plant fed by a chemical fuel
The exergy efficiency of a thermal power plant fed by a chemical fuel is slightly
smaller than its energy efficiency because the chemical exergy of the fuel is slightly
higher than its heating value:
Figure 2.6: Energy (a) and exergy (b) balance of the fluidized-bed steam boiler.
N N KE
ȘB (2.35)
BchF ĮE chF Į
However, the distribution of losses in the exergy balance is different from that
in the energy balance. The main energy loss in a steam power plant appears in
the condenser where the expanded vapour transfers the low quality waste heat to
the cooling water. In a gas-turbine power plant, the main energy loss results from
the ejection of the expanded hot gas into the environment. In both cases, the
main exergy loss is connected with the combustion process.
In a steam power plant the boiler is responsible for the low efficiency of the
plant. In a gas-turbine power plant the high exergy loss in the combustion
chamber results mainly from lowering the temperature of the working fluid
before the gas turbine (the supply of excess air, the injection of steam or liquid
water). The gas-turbine power plant provides thus better possibilities to improve
the efficiency. The irreversible heat transfer between the combustion gases and
the working fluid is eliminated. The maximum temperature of the working fluid
before the turbine is less limited. However, the irreversibility of the rejection of
waste heat to the environment is greater in the gas turbine plant because it is not
possible to realize this process isothermally.
The exergy losses in the boiler are much greater than the energy ones. The
heat stream rejected to the environment is very large, but its quality is very
low. The exergy balance indicates the causes of the large amount of waste
heat.
2.9.4. Compression refrigerator and heat pump
The main difference between the energy and exergy balance of a refrigerator lies in
the different direction of the energy and exergy flow in the refrigerated cell. The
extraction of heat from this cell means an increase of its exergy.
Example 2.11. Energy and exergy balance of a simplified steam power plant
Figure 2.7 presents a simplified scheme of a steam power plant. In fig. 2.8 the
energy and exergy balances of this plant have been compared..
Figure 2.7: Simplified scheme of a steam power plant.

Figure 2.8: Energy (a) and exergy (b) balances of a steam power plant with a
simplified scheme.
Usually, the compression refrigerator together with the electrical motors

driving the main machine and the auxiliary equipment (fans and pumps) is
included in the balance. The exergy efficiency of this complex unit may be
expressed as a ratio of real COP to COPmax of the Carnot-refrigerator:
T0 Tr 1 COP
KB Qr (2.36)
Tr EelD COPmax
where Qr = heat extracted from the refrigerated cell.

Tr = absolute temperature of the refrigerated cell.
EelD = total amount of driving electricity.
The largest exergy losses in the refrigerator result from irreversible heat
transfer. Hence, intermediate heat carriers should be avoided. One of the
advantageous working fluids in compression refrigerators is NH3. However,
ammonia is explosive and poisonous. Therefore, it cannot be applied without
an intermediate cold carrier between the machine and the refrigerated cell.
Throttling of the working fluid after condensation also causes an exergy loss.
Attempts to introduce a non-throttling cycle were not entirely successful [79].
Example 2.12. Energy and exergy balance of an ammonia compression
refrigerator.
Figure 2.9 presents a scheme of an ammonia compression refrigerator.
Table 2.5 contains the parameters of working fluid and brine. Figure 2.10
presents the energy and exergy balances of the considered installation. The
assumed ambient temperature is 20qC, and the temperature in the refrigerated
room is –1qC. The mechanical efficiency of the compressor is Km = 0.83, the
efficiency of the electrical motor KM = 0.9.
The exergy efficiency of the considered complex is 23.6%. Its value could
be increased by the application of a non-hazardous working fluid and
elimination of the intermediate heat carrier (brine).
The scheme of a compression heat pump is similar to that of a compression
refrigerator. However, usually the ‘bottom’ heat is not extracted immediately from
the ambient atmosphere. The designer looks after a bottom heat source warmer than
the ambient air, to improve the COP. Thus, a formula analogical to (1.10) should be
applied. That formula is based upon the assumption Qu = WD + Qb. It is not satisfied
Figure 2.9: Scheme of an ammonia compression refrigerator.

Table 2.5: Parameters of ammonia and brine in a refrigerator cycle
Location Flow rate Pressure Temperature

kg/s MPa qC
1 0.082 0.27 –10
2 0.082 1.1 119
3 0.082 1.1 25
4 0.082 0.27 –12
b1 16.3 – –5
b2 16.3 – –7
when we consider the complex of a heat pump together with the electrical motors
driving the main machine and the auxiliary equipment. In this case the condition
Qu < Qb +EelD appears because the heat losses of electrical motors might not be
transferred to the carrier of useful heat. The exergy efficiency of the complex of
Figure 2.10: Energy and exergy balance of an ammonia compression refrigerator.

C — compressor, Cn — condenser, T — throttling valve, E —
evaporator, Cc — cooling chamber, MElL — mechanical and
electrical losses, InL — internal exergy losses.
a compression heat pump may be based upon the assumption that only the mech-
anical losses in the machines are absorbed by the carrier of useful heat:
COP Tu T0
ȘB (2.37)
T T Tu
1 (COP Q M ) b 0
Tb
where COP = Qu/Eel D.

The exergy efficiency of a heat pump decreases when the ambient temperature
grows. The exergy efficiency is usually considerably smaller than that of the com-
pression refrigerator. It results mainly from greater exergy losses due to the
irreversible heat transfer. Additional exergy losses are introduced by the interme-
diate heat carrier between the condenser and the heated room. A large temperature
difference between the heating fluid and the heated room lowers also the exergy
efficiency.
Heat pumps are used for heating dwelling-houses. Usually the temperature of
the heating fluid is 40–50qC. A considerable improvement of the exergy efficiency
might be obtained by the introduction of a low-exergy internal installation (floor or
wall heating, low-temperature radiators) [83].
Example 2.13. Figure 2.11 presents the exergy efficiency of a compression
heat pump extracting the bottom heat from the ground with a constant temperature
of 8qC and delivering the useful heat to the room with a temperature of 20qC.
Constant values COP = 3.5 and KM = 0.9 have been assumed. At a constant value of
COP the exergy efficiency depends on the ambient temperature.
2.9.5. Sulfuric acid plant
Figure 2.12 presents the scheme of a plant producing sulfuric acid from liquid
sulfur. Figure 2.13 informs about the internal and external exergy losses
appearing in the particular parts of the plant (Rasheva and Atanasova [45]).
Figure 2.11: Exergy efficiency of a compression heat pump.

Figure 2.12: Scheme of a chemical plant producing sulfuric acid from liquid sulfur,
after Rasheva and Atanasowa [45].
The external exergy losses result from the discharge of waste products to the
environment. The largest external losses appear in the oven for burning sulfur
and in the acid cooler. The exergy losses in the oven can be decreased by a better
preheating of the combustion air (the actual temperature of the incoming air is
only 55qC), and by increasing the pressure in the oven in order to apply the gas
turbine. Internal exergy losses in the converter (where SO2 is oxidized to SO3)
are difficult to avoid. Large internal exergy losses in evaporators result from
large temperature differences between the hot gases and evaporating water. The
pressure of water might be increased to produce steam with higher parameters.
High exergy losses in the absorbers might be reduced by introducing a hot
absorption system. Hot absorption water can be produced in the coolers of acid.
The exergy efficiency of the investigated plant amounted to 55%.
According to the results presented in fig. 2.13, following main improvment
possibilities of the investigated process may be indicated [45]:
— the internal exergy losses in the oven (1) may be decreased by increasing the
temperature of the incoming combustion air; this would result, however, in
increasing the temperature of the outlet gases; in order not to increase the
internal exergy losses in the evaporator (10) it would be necessary to increase
simul-taneously the pressure of the saturated steam produced in the evaporator
(10);
— the external exergy loss in the oven (1) may decreased by combining the process
with a gas turbine utilizing the high temperature of the outlet gases; this would
require, however, an increase of the pressure in the oven;
— the internal exergy losses in the second evaporator (11) may be reduced by
increasing the parameters of the produced steam.
Figure 2.13: Exergy losses in a chemical plant producing sulfuric acid, after
Rasheva and Atanasova [45].
1 - oven for burning sulfur, 2 - converter, 3 - oleum absorber, 4 -
intermediate monohydrate absorber, 5 - final monohydrate absorber,
6 - oleum cooler, 7 - acid cooler, 8 - superheater, 9 - economizers,
10 and 11 - evaporators, 12 - heat exchangers.
— the internal exergy losses in the absorber (5) may be reduced by the use of the
hot absorption system, used for heating the supplied water.
Exercises
2.1. Calculate the temperature-dependent and pressure-dependent component of

the specific physical exergy of combustion gases containing 71.8% N2, 8.7% CO2,
17.5% H2O and 2% O2 (mol fraction). The parameters of combustion gases are p =
0.42 MPa, T = 1100 K. The specific physical enthalpy and entropy values are cited
in table 2.6. Compare the exact value of the temperature-dependent component with
the approximate value calculated by means of the mean specific heat capacity.
2.2. Calculate the specific chemical exergy of combustion gases containing
71.8% N2, 8.7% CO2, 17.5% H2O and 2% O2 (mol percent), assuming standard
environmental parameters. Calculate the ratio of chemical exergy to the
temperature-dependent component of the physical exergy determined in exercise
2.1.
2.3. Calculate the specific physical exergy of steam with the parameters p = 14
MPa, T = 560qC. The ambient parameters are p0 = 98 kPa, T0 = 293 K.
2.4. Calculate the specific physical exergy of liquid ammonia with the
temperature of –15qC. Assume standard ambient parameters.
2.5. Calculate the mol fraction of SO2 in atmospheric air assuming standard
Table 2.6: Parameters of the components of combustion gases
Component Amount Specific physical Specific physical Specific heat

of moles enthalpy entropy capacity
J/mol J/(mol K) J/(mol K)
N2 0.718 24 671 39.592 30.768
CO2 0.087 38 776 60.587 48.358
H2O 0.175 30 118 47.906 37.560
O2 0.020 26 215 41.736 32.693
environmental parameters and the thermodynamic equilibrium between SO2 and the
reference species. The standard normal exergy of SO2 is cited in table I.
2.6. Calculate the standard chemical exergy of Ca2SiO4 if the standard free
energy of formation is known, 'f G0 = 2191.6 kJ/mol. The standard values of the
chemical exergy of the elements are cited in table I, at the end of this book.
2.7. Calculate the standard chemical exergy of the element B from the data
concerning the reference species cited in table 2.2.
2.8. Calculate the standard free energy increase for the reaction
CaO + SO2 + 0.5 O2 o CaSO4
using the values of standard chemical exergy cited in table I.

2.9. Calculate the maximum work of the reaction
CaCO3 + N2 + 2.5 O2 o Ca(NO3)2 + CO2
assuming the normal environmental temperature, standard partial pressures of

the gaseous substances, pure CaCO3 and Ca(NO3)2. Notice that by means of this
reaction work could be produced by means of the common components of the
environment (CaCO3, O2, N2, CO2), if the irreversibility of the cited reaction
could be sufficiently reduced.
2.10. Calculate the specific chemical exergy of bituminous coal with the
following composition (mass percent): zC = 55%, zH2 = 4%, zO2 = 8%, z N2 = 1%, zS
= 2%, zw = 10%, za = 20%. The lower heating value is 24 880 kJ/kg. Assume that
ash contains only SiO2. Use standard ambient parameters.
2.11. Calculate the standard chemical exergy of liquid freon CHFCl2 by means
of the contribution method of chemical groups (see table II, Appendix).
2.12. Calculate the standard chemical exergy of steel with the following
composition (mass percent): zFe = 98%, zC = 0.6%, zMn = 0.7%, zS = 0.3%, zP =
0.1%, zSi = 0.3%.
Assume that carbon appears in the form of Fe3C and Mn3C.
2.13. Calculate the exergy efficiency of a coal-fueled boiler heating the network
water from 50qC to 110qC. The energy efficiency of the boiler amounts to 0.86. The
ambient temperature is –10qC. Take the ratio of the chemical exergy to the lower
heating value of coal from table 2.4.
2.14. Calculate the exergy efficiency of a coal-fueled boiler producing steam
with the parameters p = 14 MPa, T = 560qC. The feeding water has a temperature of
240qC. The energy efficiency of the boiler amounts to 0.93. The ambient
temperature is 10qC. Take the ratio of the chemical exergy to the lower heating
value of coal from table 2.4.
2.15. An absorption heat pump operates as an auxiliary part of a geothermal
heating system. Calculate its exergy efficiency. The driving heat is delivered by
means of hot water with initial and final temperature Tw1 = 160qC, Tw2 = 80qC. The
energy efficiency of the considered heat pump is characterized by COP = 1.6. The
bottom heat is extracted from the preliminarily utilized geothermal water cooled
down in the heat pump from 42 to 27qC. The useful heat is delivered to the network
water to heat it fromss 40 to 78qC. The ambient temperature is –5qC.
Chapter 3
Cumulative exergy consumption and partial

exergy losses
3.1. Definition of cumulative exergy consumption (CExC)
Consumption of exergy connected with the fabrication of some considered product

appears not only in the plant manufacturing the product, but also in all plants
delivering semi-finished products and raw materials for the final production process.
The total consumption of the exergy of natural resources connected with the
fabrication of the condidered product and appearing in all the links of the network
of production processes, has been called cumulative consumption of exergy CExC
[67].
The analysis of the cumulative consumption of exergy can be considered as
a development of the analysis of the cumulative consumption of primary energy.
The definition of the cumulative consumption of energy or exergy is similar to
that of the economic cost. Therefore, the first authors analyzing the cumulative
consumption of energy introduced the term energy cost [11–13]. Monographic
books presenting the problem of cumulative consumption of energy have been
elaborated [6, 8].
An essential difference between the analysis of the cumulative consumption
of energy and exergy should be stressed. The first one does not give any
possibility of determining the influence of the imperfection of particular partial
processes on the final result of the analysis, whereas the second enables us to
determine partial exergy losses appearing in particular links of the considered
system and so indicates the possibilities for the improvement of the chain of
constituent processes.
The CExC-values can be calculated separately for each particular kind of
primary exergy or may comprise the sum of values of the non-renewable primary
exergy or the sum of all the values of the primary exergy. Usually the second
method is applied. When calculating the partial exergy losses appearing in the
particular links of the energo-technological network, the calculations of CExC
should comprise all the natural resources of exergy, the renewable and non-
renewable ones, because it is impossible to distinguish which exergy losses are
connected with the renewable and separately with the non-renewable exergy
resources.
CExC can be calculated by means of process analysis (sequence method) or
by means of a set of balance equations. Process analysis (sequence method)
begins in the final link of the fabrication of the considered product and runs
through the processes of producing semi-finished products, the fabrication of
machines and equipment until the extraction of raw materials from natural
resources. The sequence method enables us to analyze only one product, but can
be applied if the connections between the considered links of the technological
network are weak (the consumption of the considered product in preceding links
is small). The method of balance equations is more general. It requires more
work because need for the formulation and solution of the set of balance
equations. The balance equations based upon the statement that the CExC-value
burdening the useful products of the process results from the sum of CExC-
values characterizing the delivered materials, semi-finished products and energy
carriers.
3.2. The problem of CExC of the human work

Some authors try to introduce the CExC of human work into the calculation of
CExC of useful products [43]. However, the CExC of human work results from the
total consumption of the primary exergy in the considered region. The sum of all
the values of CExC burdening the human work equals the total consumption of the
primary exergy. When calculating the CExC values burdening particular useful
products, the CExC values burdening the used materials, semi-finished products and
energy carriers are additionally introduced into the calculations. Hence, the
consumption of primary exergy appears twice in the calculations.
Szargut [76] elaborated a simple proof that it is not necessary to take into
account the human labor when calculating the CExC-value because it would
denote a double introduction of the same quantity. The mentioned statement
results, for example, from the analysis of a simple system as presented in fig. 3.1.
The system contains coal mines, industry and the consumption sector. Some part
Ck of the produced coal is consumed immediately. The remaining part Ci is used
in industrial processes. The consumption of industrial products in coal mines is
Ic. In order to simplify the mathematical proof, the cumulative con-sumption of
all the kinds of the primary exergy has been taken into account.
If we introduce the cumulative consumption of exergy burdening the human
work into the balance equations, we obtain for the analyzed system:
bc* bc ( I c C )bi* lc r , (3.1)
bi* (Ci / I )bc* li r , (3.2)
where bc* , bi* = CExC-value burdening a unit of coal and of the industrial product
bc = specific exergy of coal
lc,li = specific consumption of human labor in coal mines and industry
CUMULATIVE EXERGY CONSUMPTION AND PARTIAL EXERGY LOSSES 59
Figure 3.1: Scheme of a simplified system.
r = CExC-value burdening a unit of human labor

Ci,Ic = consumption of coal in industry and of industrial products in coal
mines
C,I = total production of coal and industrial products.
From eqns (3.1) and (3.2) it results:
bc > lc ( I c / C )li @ r
bc* (3.3)
1 ( I c / I )(Ci / C )
The total consumption of primary exergy can be expressed as:

bi* I k bc*Ck bi* ( I I c ) bc* (C Ci ) Cbc ( Lc Li )r (3.4)
where:
Lc lc C , Li li I . (3.5)
On the other hand, it is evident that the total consumption of primary exergy
is Cbc. So the balance of CExC is closed, if the quantity r does not appear in eqns
(3.1) and (3.2). Hence, the mentioned statement is correct.
3.3. A set of input-output equations

The balance equation of CExC is based upon the statement that the CExC-value of
the product of some considered link results from the CExC-values burdening the
semi-finished products and by-product, and from the exergy of natural resources
extracted from nature in the considered link. The set of balance equations takes
the form [67]:
b*j ¦ f uj bu* ¦a b ¦a *

ij i
*
b Ej
uj u (3.6)
u i u
where b*j , bi* , bu* = specific CExC-value burdening the major product of the jth
and ith process, and the uth by-product
aji,auj = coefficient of consumption of the ith semi-finished product
and uth by-product per unit of the jth product
fuj = coefficient of the by-production of the uth by-product per unit
of the jth major product
Ej = exergy of the natural resources extracted from nature in the jth
process, per unit of the jth product.
The terms representing the production and consumption of the by-products
can be replaced by terms containing CExC of the ith major product substituted
by the uth by-product, according to the principle of avoided expenditures (the
by-product should be burdened with the consumption of semi-finished products
and energy carriers avoided in the substituted process thanks to the utilization of
the considered by-product)
fij aij
f uj , auj , ȡu ȡi siu (3.7)
siu siu
where siu denotes the replacement ratio in units of the ith major product replaced
by a unit of the uth by-product.
After introducing (3.7), eqn (3.6) takes the form:
b*j ¦ ( fij aij )bi* ȕj (3.8)

i
The consumption of machines and installations can be also taken into account in
eqn (3.8), using their consumption coefficient:
mij
aij (1 ui ) (3.9)
W iG j
where mi = number of ith machines or installations participating simultaneously

in the fabrication of the jth product
Gj = annual production of the jth product
Wi = life time of the ith machine or installation
ui = fraction of the value bi* which might be recovered by the use of
secondary raw materials remaining after the wear of the considered
machine or installation [15, 16].
3.4. Cumulative exergy efficiency
When considering the production of materials or energy carriers, the cumulative

exergy efficiency CExE (or the cumulative degree of perfection CDP) of the total
chain of processes leading from the natural resources to the considered product can
be expressed by means of the ratio of useful exergy to the cumulative consumption
of driving exergy:
bu
Ș*B (3.10)
bD*
The cumulative consumption of exergy should in this case take into account all the
kinds of primary exergy (non-renewable and the renewable ones). CExC should be
calculated in a globally. Exemplary values of CExE are cited in table 3.1.
CExE can be expressed in the form of the product of component efficiencies
when the chain of production processes leading to the considered product does
not contain strong feedbacks. Weak feedbacks can be taken into account by
means of an iterative procedure.
Example 3.1. The immediate exergy efficiency of some power plant fed
with hard coal amounts to KBel = 0.36. The CExE value should additionally take
into account the cumulative efficiency of fuel delivery (extraction and
transportation) Ș*df , the efficiency of transformation and transmission of
electricity Ktr and the cumulative exergy investment efficiency Ș*B inv (taking into
account the consumption of materials and energy burdening the construction of
the power plant. The consumption of electricity connected with the delivery of
fuel and the construction of the plant is not high; thus the product of partial
efficiency values can be applied:
nB* el ȘB el Ș*df Ștr nB* inv (3.11)
The cumulative efficiency of investments can be expressed as follows:
B *f Ĳt
Ș*B inv (3.12)
B *f Ĳt ¦ Binv
*
i
i
where B *f = rated cumulative consumption of fuel exergy, per time unit

Wt = total operation time of the plant with rated power
*
B = cumulative consumption of the primary exergy burdening the con
inv i
struction of the particular parts of the plant.

Usually the investment efficiency is neglected when calculating CexE.
Assuming in the considered example Ș*df = 0.93, Ktr= 0.9, Ș*B inv = 0.96 we
obtain Ș*B el = 0.29.
CExE can be calculated also for the by-products; according to the principle
Table 3.1: Exemplary values of CExC and CexE.
Material Units in
Columns
Name Exergy b 2, 4 CExC CExE % Notes
1 2 3 4 5 6
Bituminous coal 1.09 HL MJ/kg 1.12 HL 93.1

Lignite 1.17 HL MJ/kg 1.20 HL 92.3
Metallurgical 1.06 HL MJ/kg 1.35 HL 74.2
Coke
Natural gas 1.04 HL MJ/kmol 1.06 HL 91.5 high CH4 content
Gasoline 1.07 HL MJ/kg 1.32 HL 80.8
Electricity 1 J/J 3.40 29.4 from bituminous
coal, energy
efficiency 36%, at
the place of
consumption
Oxygen for 3.4 kJ/mol 237 1.4 not compressed
Metallurgy
Pig iron 8.75 MJ/kg 28.6 30.6 liquid
Converter steel 8.04 MJ/kg 26.7 30.1 liquid, 15% scrap
Electric steel 8.04 MJ/kg 22.8 35.4 liquid, 100% scrap
Steel pipes 7.04 MJ/kg 58.7 16.0
Hot-rolled steel 7.04 MJ/kg 37.05 19.0 40% scrap in raw
materials
Cold-rolled steel 7.04 MJ/kg 47.6 14.8 40% scrap in raw
materials
Copper 2.11 MJ/kg 147.4 1.4 electrolytic, from
Cu2S
Zinc 5.19 MJ/kg 125.8 4.1 electrolytic, from
ZnS
Aluminium 32.9 MJ/kg 250.2 13.2 electrolytic, from
Al2O3
Sulfur 19.01 MJ/kg 30.2 62.9 bore-hole method
Ammonia 19.84 MJ/kg 48.2 41.1 semi-combustion
of natural gas
Sulfuric acid 1.67 MJ/kg 11.1 15.0 from sulfur
Methanol 22.41 MJ/kg 73.1 30.7
Glass 0.174 MJ/kg 33.4 0.5 panels
Cellulose 16.45 MJ/kg 60.0 27.4 from wood,waste
products used as
fuels
of avoided expenditures it should be done by means of CExE of the replaced

product and the exergy replacement ratio:
Ș*B s
Ș*Bu (3.13)
S B su
where K*B s = CExE of the production of the replaced major product

sB su = exergy replacement ratio, in units of exergy of the sth replaced
major product per unit of exergy of the considered by-product.
Usually the replacement ratio is less than 100% and the CExE of the by-
product is greater than the CExE of the replaced major product. It denotes that
the by-product should be burdened with a decreased consumption of driving
exergy of the considered complex process, and a greater part of driving exergy
should burden the major product, respectively. The cumulative driving exergy
consumption B *D m burdening the major product of the complex process can be
Bu
*
BDm BD* ¦ (3.14)
u Ș*Bu
where BD* is the cumulative driving exergy of the complex process.

Hence, CExE characterizing the fabrication of the major product results
from the relation:
Bm
Ș*Bm (3.15)
Bu
BD* ¦
u Ș*Bu
where Bm, Bu are the exergy of the major product and of the uth by-product.
Example 3.2. Blast furnace gas (the by-product of the blast furnace process)
can be used in heating ovens of steel plants. In this case it substitutes for the
natural gas, but the exergy substitution ratio is smaller than 100% because blast
furnace gas contains a greater fraction of non-combustible components, which
decreases the efficiency of the heating oven. The exergy replacement ratio of
natural gas by blast furnace gas amounts to about 85%. The CExE of the deli-
very of natural gas is about 87%. Hence, the CExE of the production of blast
furnace gas amounts to 102%. The value exceeding 100% has only a mathe-
matical meaning and should be used in calculations of the CExE burdening the
production of liquid pig iron.
3.5. Cumulative and partial exergy losses
The difference between the CExC-value and the exergy of the considered product
can be partitioned into partial exergy losses PEL appearing in the particular links of
the network of production processes [74]. Such a partition is possible if the
calculation of CExC comprises all the kinds of exergy extracted from nature, i.e.
taken from non-renewable or renewable domestic or foreign sources:
b*j b j ¦ įbkj (3.16)

k
where b*j = specific cumulative consumption of exergy burdening the jth product
G bkj = partial exergy loss connected with the fabrication of the jth product
and appearing in the kth link of the network of production processes.
The analysis of the partial exergy losses indicates possibilities of de-
creasing the CExC-value. It can be attained by improving the links with great
PEL-values, by changing the technology of production of some semi-finished
products or by changing the kind of some semi-finished products. Partial
exergy losses can be calculated only in a global scope or for products fabri-
cated without a considerable consumption of imported materials and energy
carriers.
When analyzing the partial exergy losses, all the kinds of the primary
exergy should be taken into consideration, including the renewable ones. The
partial exergy losses cannot be divided into losses connected with non-re-
newable and renewable kinds of the primary exergy. Domestic and imported
semi-finished products and energy carriers cannot be distinguished either.
Hence, the analysis is based upon the determination of the cumulative
consumption of exergy performed in a global scope.
The analysis of partial exergy losses makes it possible to evaluate
quantitatively the deleterious impact of all irreversible phenomena appearing
in the energy- and technological network as a result of the fabrication of the
considered product. Hence, we obtain complete information about the thermo-
dynamically allowed possibilities of improving the network to decrease the
consumption of primary exergy. This improvement can comprise the reduction
of the irreversibility of most imperfect component processes, a change of the
technology or a change of the applied semi-finished products and energy
carriers.
The analysis of partial exergy losses should not be excessively detailed
because this would decrease the clearness of the results. The partial exergy
losses appearing in the links preceding the final link can be determined without
any partitioning into more detailed components and can even be cumulated
with exergy losses appearing in previous processes.
3.6. Net coefficients of consumption
The coefficients of consumption aij,Ej appearing in eqn (3.8) refer to a unit of

the major jth product and include by-products. For example, in a heat-and-
power plant the coefficient of coal consumption relates to a unit of useful heat
together with the cogenerated amount of electricity. To calculate partial exergy
losses the net coefficients of consumption of semi-finished products and natural
resources should be determined [74]:
Aij aij ¦ f pj Aip (3.17)

p
ȕ Nj ȕ j ¦ f pj ȕ N p (3.18)
p
where Aij,Aip = coefficient of net consumption of the ith product per unit of the
jth and pth major product
ENj,ENp = coefficient of immediate net consumption of natural resources per
unit of the jth and pth major product.
Eqns (3.17), (3.18) can be presented in a matrix form:
A a ( E f ) 1 , BNT B T ( E f ) 1 (3.19)
where E is a unitary diagonal matrix.

The coefficients of net consumption can be used to calculate of the CExC-
values similarly as the coefficients of gross consumption:
b*T BNT ( E A) 1 (3.20)
We can check the correctness of eqns (3.19) introducing them into eqn (3.20):
b*T [ E a ( E f ) 1 ] B T ( E f ) 1 (3.21)
Multiplying eqn (3.21) by the matrix (E+f) we obtain the formula (3.8).
The local net exergy loss GbNj related only to a unit of the major product of
the jth process, results from the exergy balance of the jth process. It comprises
the internal and external exergy losses:
¦ A b ȕ
i
ij i Nj b j įbNj (3.22)
or in a matrix form:
bT ( E A) BNT GBNT (3.23)
Partial net exergy losses result from the cumulative consumption of particular
products per unit of the considered product:
įbNkj S Nkj įbNk (3.24)
where SNkj denotes the cumulative net consumption of the kth product per unit of
the jth product.
The value of SNkj results from the matrix relation:
SN ( E A) 1 (3.25)
The sum of partial exergy losses fulfils eqn (3.16).

Example 3.3. Calculating the partial exergy losses connected with the
production of coke and liquid pig iron, a simplified system comprising a coal
mine, an iron-ore mine, a source of natural gas, a power plant, a coking plant,
an ore-sinter plant and a blast furnace plant has been investigated [73]. The
coking plant is equipped with a dry-quenching installation and a steam
turbine driving an electrical generator. The mentioned plants have only weak
connections with other industrial plants. Four by-products appear in the
considered system: coke-oven gas, tar and electricity produced in the coking
plant and blast-furnace gas. It has been assumed that the coke-oven gas and
tar substitute the natural gas in a proportion of 0.514 kmol n.g./kmol c-o.g.
and 0.0499 kmol n.g./kg tar. The basic part of the blast-furnace gas sub-
stitutes natural gas in a proportion of 0.114 kmol n.g./kmol b-f.g. The peak
part of the produced blast-furnace gas is burnt in the boiler house and
substitutes a hard coal in the proportion 3.62kg coal/kmol b-f. g. The
consumption of steel in coal mines has been substituted by the consumption
of pig iron.
The following values of specific exergy and of the coefficients of con-
sumption and by-production have been assumed (the mentioned values of the
substitution ratio have been taken into account):
(1) Coal mine b1 = 24.7 MJ/kg,

a11 = 0.0058 kg/kg, a31 = 0.000041 kmol/kg, a41 = 0.175 MJ/kg,
a71 = 0.004 kg/kg,
(2) Iron-ore mine b2 = 0.35 MJ/kg,
a32 = 0.00023 kmol/kg, a42 = 0.0735 MJ/kg
(3) Extraction of natural gas b3 = 802 MJ/kmol,
a43 = 4.17 MJ/kmol.
(4) Power plant b4 = 1 MJ/MJ, a14 = 0.156 kg/MJ.
(5) Coke plant b5 = 28.95 MJ/kg,
a15 = 1.60 kg/kg, a35 = 0.00458 kmol/kg, f35 = 0.0112 kmol/kg,
a45 = 0.0958 MJ/kg, f45 = 0.391 MJ/kg.
(6) Ore sinter plant b6 = 0.73 MJ/kg,
a26 = 0.827 kg/kg, a36 = 0.0002247 kmol/kg, a46 = 0.1073 MJ/kg,
a56 = 0.0612 kg/kg.
(7) Blast furnace plant b7 = 8.75 MJ/kg liquid pig iron,
a17 = 0.0366 kg/kg, f17 = 0.0214 kg/kg, a27 = 0.206 kg/kg
a37 = 0.00441 kmol/kg,
f37 = 0.00549 kmol/kg, a47 = 0.0568 MJ/kg, a57 = 0.571 kg/kg
a67 = 1.594 kg/kg.
Calculation results of partial exergy losses connected with the

production of coke and pig iron are presented in table 3.2.
Table 3.2: Partial net exergy losses connected with the production of coke and
liquid pig iron (in % of CExC).
Partial
net
Material Process Coefficient of consumption
exergy
gross net unit loss
aij – fij Aij %
Coke coal mine 1.600 1.539 kg/kg 1.803

iron ore mine – – – 0.007
natural gas extraction –0.00602 0.0011 kmol/kg 0.002
coking plant 11.128
power plant – – – 2.918
sinter plant –0.2952 0.0677 MJ/kg 0.048
blast furnace plant – – – 0.160
cumulative degree of – – – 83.934
perfection
Pig iron coal mine 0.0152 0.0366 kg/kg 1.802

iron ore mine 0.206 0.206 kg/kg 1.577
natural gas extraction –0.00108 –0.0038 kmol/kg 0.077
coking plant 0.571
power plant 0.0568 0.571 kg/kg 10.251
sinter plant 1.594 0.0327 MJ/kg 6.684
blast furnace plant – 1.594 kg/kg 10.351
– – 34.315
cumulative degree of – – – 34.943

perfection
3.7. Sequence method for the evaluation of partial exergy losses
The sequence method of the determination of PExL consists in the analysis of the
subsequent links of the energy- and technological network, beginning with the final
link and ending with the extraction of primary exergy from natural resources. It is
convenient to present the results by means of a graphical scheme [25, 81]. The
network can be divided into some levels [6]. On the first level the immediate
consumption of semi-finished products and energy carriers in the final stage of the
production is analyzed, including the consumption of energy for trans-

portation. On the second level the fabrication of semi-finished products and
energy carriers for the first level should be considered, taking into account
the immediate consumption of semi-finished products and energy carriers
for this purpose, together with their transportation. On the third level the
fabrication of machines and installations for the first level should be
analyzed. The fourth level takes into consideration the fabrication of mach-
ines and installations for the production of machines and installations
operating on the first level, together with the production of semi-finished
products and energy carriers for the third level. The analysis of cumulative
indices finishes usually on the second level.
The application of the sequence method is easier if the values of CExC
are known for the principal materials and energy carriers (for example, for
hard coal and lignite, natural gas, coke-oven gas, pig iron and steel) [82].
The values cited by Szargut and ZiĊbik [81] change with the development
of technology. The knowledge of the mentioned data permits the intro-
duction into the sequence analysis the values of the CExL burdening the
principal materials and energy carriers. A more detailed partitioning of these
losses would require the use of the results of the sequence analysis of the
production of principal materials and energy carriers.
Example 3.4. Sequence analysis of the single-purpose production process.

The sequence analysis of PExL in the production process with a single-
purpose final link, has been presented for the example of calcium carbide.
The results of the sequence analysis of cumulative energy consumption,
cited in [6] have been used. The following principal materials and energy
carriers appear in this process: hard coal, coke, electricity and limestone.
The graphical scheme of the sequence analysis of PExL is presented in Fig.
3.2. The summarized values are cited in Table 3.3. It contains the CExL
burdening the production of electricity and coke. Therefore, the PExL-value
determined for the extraction and transportation of hard coal relates only to
the coal used for the production of electrodes. For the delivery of electricity
and coke the CExE-values have been accepted (25.8% and 74.3%).
Example 3.5. Sequence analysis of the cogeneration process.

PExL in the cogeneration process were analyzed on the example of
the production of network heat in a steam HP-plant [72]. The process
substituted by the fabrication of a by-product (electricity in the considered
case) was left out of consideration by means of the exergy balance
formulated with the use of the net coefficients of the consumption burden-
ing the production of heat only, eqn (3.17). The net consumption Pq of coal
(per unit of time) burdening the production of heat results from the
produced electric power and energy efficiency of the replaced power plant.
If it can be assumed, that the efficiency of electricity transmission and
delivery of coal is the same for the HP-plant and the substituted power
plant, the following formula can be used:
Figure 3.2: Scheme of the sequence analysis of CExC and PExL for the
production of calcium carbide [81].
N el
Pq P (3.26)
H L ȘEel
where P , Pq = total flow rate of coal consumed in the HP-plant and flow rate
burdening the production of heat
KEel = energy efficiency of the replaced power plant
HL = lower heating value of fuel.
It has been assumed that the electricity driving the network pumps is taken
from the electrical network. The assumed heat losses in the main heating network
are 15%, in the local network 2%. Per 1 GJth delivered to the consumers, 1.2 GJth
should be produced in the HP-plant. The ratio of chemical exergy of coal to its
lower calorific value is 1.09. The assumed water losses in the heating network per
1 h are as high as 0.7% of the volume of the pipes, the mean transportation distance
is 4km, the pipe diameter 0.3m, the main thermal power delivered to the
consumers is 35 MWth. The steel consumption for the maintenance of the pipes
Table 3.3: Partial exergy losses in the production of calcium carbide.
Coefficient of cumulative Partial exergy

consumption loss
Process in units of
in natural exergy %
units per 1 t MJ/t MJ/t of
of carbide carbide carbide CExC
Extraction and delivery of
coal for the production
of electrodes . . . . . . . . 56 kg 1495 85 0.11
Production of coke . . . . 853 kg 31 475 8121 10.23
Production and
transmission of electricity. 3289.7 kWh 46 081 34 238.1 43.13
Extraction and delivery
of lime stone. . . . . . . . 1845 kg 334 33.4 0.04
Production of electrodes.. 37 kg 1645 196.5 0.25
Burning of lime . . . . . . . 985 kg 6692 2987.6 3.76
Production of carbide . . . 1000 kg 79 385 10 813.5 13.62
Exergy and cumulative – – 22 910 28.86
exergy efficiency. . . . . . .
results from an assumed durability of 10 years. The CExC value for the
production of steel pipes is 60 MJ/kg. The driving power of the pumps is 160
kW in the main network and 80 kW in the local network.
The graphical scheme in fig. 3.3 relates to the mean ambient tempera-
ture during the heating season in southern Poland. The calculation of exergy
losses in the heat exchangers is based upon the following assumptions:
— temperature of steam condensation 104qC,

— temperature of hot and return water in the main network 78/42qC,
— temperature of hot and return water in the local network 53/42qC,
— temperature of the heated rooms 20qC.
Similar calculations were performed for other values of the ambient

temperature, assuming a constant ratio 0.27 of the counter-pressure power to
the gross amount of heat. Table 3.4 contains the results of calculations. The
PExL values burdening the production of electricity for driving the pumps
have been cumulated. Similarly the CExL values connected with the delivery
of coal for production of heat and burdening the production of steel are
presented.
Figure 3.3: Scheme of the sequence analysis of CExC and PExL in the
production of heat in the HP-plant [72].
Table 3.4: Partial exergy losses in the production and delivery of heat from a steam
HP-plant, for the heating of rooms (in % of cumulative consumption of
exergy).
Ambient temperature, qC
Process
–20 –11 –5 +2 +6 +12
Extraction and transportation of coal
for the production of heat . . . . . . . 5.1 5.2 5.4 5.6 5.8 6.2
Production of heat in the HP-plant . . 56.6 51.0 56.7 63.1 66.0 68.1
Production of electricity
for driving the network pumps . . . 2.8 3.4 3.7 4.2 4.5 6.4
Heat transfer in the main heat
exchangers and transportation of
heat in the main network. . . . . . . . . 9.3 13.2 13.0 12.4 12.7 13.0
Heat transfer in local heat
exchangers and transportation of
heat in the local network . . . . . . . . 4.3 4.7 3.8 3.1 2.4 1.6
Heat transfer in the internal
installation . . . . . . . . . . . . . . 11.1 11.9 9.2 6.0 4.3 2.1
Production of steel for the
maintenance of pipes . . . . . . . . . . 0.7 0.8 0.9 1.0 1.1 1.2
Cumulative exergy efficiency 10.1 9.8 7.3 4.6 3.2 1.4
Exercises
3.1. A compressor heat pump applied for the heating of rooms has the
energy index COP = 3.5. The required temperature in the heated rooms is 22qC.
The mean ambient temperature is 2qC. The cumulative exergy efficiency of the
delivery of electricity is 0.29. Calculate the mean cumulative exergy efficiency
of the considered heat pump.
3.2. Calculate the cumulative exergy efficiency of the absorption heat pump
considered in exercise 2.15. Assume that the driving heat is produced in a boiler
fired with natural gas. Its energy efficiency is 0.88.
3.3. The cumulative exergy consumption burdening the production of hot-
rolled steel tubes is 0.587 MJ/kg. The specific chemical exergy of steel is 7.04
MJ/kg. Calculate the cumulative exergy efficiency of the production of steel tubes.
3.4. The coal-fired steam HP plant equipped with a back-pressure steam
turbine produces useful heat and electricity. The proportion of the produced
electric power and thermal power is 0.3. The useful heat is absorbed by the
network water heated from 55 to 110qC. The energy efficiency of the HP plant
amounts to 0.9. The ambient temperature is –8qC. The cumulative exergy effi-
ciency of the delivery of electricity from a replaced condensation steam power
plant is 0.29. Calculate the cumulative exergy efficiency of the production of

useful heat.
3.5. Calculate the CExE for the production of methanol if the cumulative
consumption of energy per ton of CH3OH was: 3308 MJ of electricity, 6082 MJ of
heat, 554 MJ of the chemical energy of coke, and 45,348 MJ of the chemical energy
of natural gas (expressed by the lower heating value). For fuels assume the values
bch* H L from table 3.1. For electricity delivery Ș*B = 0.29 and for heat production
Ș*B = 0.4. For the heat carrier the mean thermodynamic temperature Th = 425 K,
the ambient temperature T0 = 283 K.
3.6. Calculate the partial exergy losses connected with the production of
methanol.
3.7. Calculate the CExE for the production of ZnO-sinter if the consump-
tion of energy and raw materials per ton ZnO was: 2076 MJ of electricity, 19,393
MJ of the chemical energy of bituminous coal, 48,649 MJ of the chemical energy
of coke (chemical energy expressed by the lower heating value), 0.0077 t of hot-
rolled steel, 0.003 t of iron casting. For fuels assume the values bch* / H L from
table 3.1. For electricity delivery Ș*B = 0.29. For iron casting assume the value
bch= 8200 MJ/t, Ș*B = 0.161.
Chapter 4
Practical rules for improving thermodynamic

imperfection
The more rational utilization of energy is one of the cheapest methods of
satisfying the energy demand of humankind. The aim of energy conservation is
to satisfy all the demands for final energy by means of a smaller consumption
of primary energy. The following main methods of energy conservation may be
named:
(1) reduction of the thermodynamic imperfection of energy processes,
(2) improvement of the efficiency of energy-consuming installations and devices,
(3) improvement of the operation of energy-consuming installations and devices,
(4) improvement of the utilization of waste energy,
(5) decrease of the consumption of materials,
(6) decrease of the fraction of energy-consuming products in the overall industrial
production,
(7) improvement of the utilization of secondary materials obtained due to the wear
of useful products.
The solution of the first problem should be based on the principles of ex-
ergy analysis. Sama, Quian and Gaggioli proposed 13 common-sense 2nd Law
guidelines ensuring the reduction of the thermodynamic imperfection of thermal
processes [48]. These guidelines were supplemented by Szargut. The additional
rules take into account the mutual influence of the particular links of energy
systems. So, a set of 20 practical rules (or guidelines) have been formulated [75]:
1. Accept exergy losses only if they are indispensable for the reduction of
investment expenditures. Exergy losses without any economic justifica-
tion should be treated as the result of an engineer’s error.
For example, exergy losses due to irreversible heat transfer cannot be eli-
minated from a heat exchanger because without temperature differences the
heat transfer area would be infinitely large. On the other hand, the practical
realization of a thermal process might deviate from the formulated rules if it
were economically justified.
2. Do not use excessively large or excessively small thermodynamic driving

forces of the process operation.
For example, the temperature differences between the heating and the heated
fluid within a heat exchanger should not be too small (because the necessary
heat transfer area would be too large) and not too large (because the efficiency
of the entire process would be excessively reduced). The temperature differ-
ence between the heating and the heated stream should be approximately
proportional to the absolute temperature.
3. Minimize the mixing of streams with differences in temperature, pres-
sure or chemical composition.
The mixing of streams with different temperatures is equivalent to an ir-
reversible heat transfer. The mixing of streams with different compositions
appears, for example, in the production of air enriched with oxygen when
technical oxygen (produced with a large consumption of driving energy) is
mixed with atmospheric air. The immediate enrichment method would be
thermodynamically more correct, but until today such methods are too ex-
pensive. In the chemical industry every recirculation of the exhausted material
increases also the entropy generation and worsens the quality of the initial
material.
An important example of mixing streams with different compositions and/or
temperatures appears in the recirculation process of the intermediate or outlet
product. In many processes of chemical technology recirculation is used for a
better utilization of the useful component contained in the outlet waste
product. However, in this case the recirculation reduces the concentration of
the active components in the inlet material, causing an increase of the
necessary area or volume of the apparatus.
In some processes the expected effect of recirculation is more important than
the involved exergy loss. For example, the recirculation of combustion gases
is applied in combustion processes to decrease the temperature and to reduce
the formation of nitric oxides. However, as a negative effect, the mean
temperature difference between the combustion gases and the heated matter
becomes smaller, and that leads to an increase of the necessary heat transfer
area.
Another example of an unavoidable recirculation can appear in a suspension
dryer. The necessary volumetric stream of the drying gas can be too small for
the formation of a suspension of the dried solid particles. To attain a sufficient
velocity of the drying gas, its recirculation can be applied.
Example 4.1. Figure 4.1 presents the scheme of a set of reactors in the process
of esterification of acrylic acid by means of methyl alcohol. Every reactor operates
with evaporation of the reactants. The active components (alcohol + acid + cata-
lyzer) are separated from the vapour by condensation and turned back to the inlet
of every reactor. Additionally, some part (up to 50%) of the exhausted fluid is
recirculated from the outlet of the system to its inlet, to reduce the loss of the not
PRACTICAL RULES FOR IMPROVING THERMODYNAMIC IMPERFECTION 77
Figure 4.1: A set of reactors for the esterification of acrylic acid by means of
methyl alcohol. Si , Wi — stream of the inlet- and outlet-fluid of the
ith reactor, al+ac+ct — alcohol+acid+catalyzer, Ci — condenser and
separator of the ith reactor, D — distributor, g — recirculation ratio.
utilized reactants. However, the concentration of the active reactants in the inlet
fluid becomes smaller after recirculation, and the necessary volume of the reactors
gets larger [108].
Example 4.2. The high temperature of the working fluid entering the gas
turbine requires the cooling of the turbine blades. Usually an open system of
cooling is applied. The compressed air taken from the outlet of the compressor
(sometimes additionally cooled in an external cooler) flows in the channels
inside the blades. The cooling air flowing out from the cooling channels (with -
an open outlet) mixes with the working fluid. The blade cooling decreases the
efficiency of the turbine. The irreversible mixing of the cooling air with work-
ing fluid is the main cause of the efficiency decrease [89].
4. Do not discard heat at high temperature to the ambient or the cooling
water and do not heat the refrigerated stream with hot streams or with
hot water.
High-temperature waste heat has a positive exergy which should be utilized.
The exergy of the refrigerated streams is also positive and may be utilized
by the heat exchange with subambient process streams that need to be
cooled.
Example 4.3. Hot-rolled products in steel plants are usually cooled in open
air. So their physical exergy is lost. In some plants the cooling process is per-
formed within a chamber equipped with water-cooled walls where hot water or
steam can be produced.
Example 4.4. Liquid natural gas (LNG), after transporting by ship, should
be evaporated before its pipeline transportation. The evaporation heat is usually
taken from the environment. It is possible to utilize the physical exergy of LNG,
for example for the production of electricity. In this case the atmospheric air
would be a higher heat source, and LNG would represent the lower heat source.
The suitable cycle of the power plant might be realized by means of a substance
having a critical temperature higher than the ambient one and its condensation
pressure corresponding to the temperature of LNG—slightly higher than the
ambient one.
5. All counter-current processes are generally thermodynamically more
efficient than parallel ones.
For example, at the same heat-transfer area the counter-flow heat exchanger
ensures a higher temperature increase of the heated fluid than the parallel-
flow heat exchanger. At the same amount of transferred heat a parallel-flow
heat exchanger requires a greater heat transfer area than the counter-flow
heat exchanger. The application of the parallel current is acceptable only if
the wall temperature in the heat exchangers has to be reduced or if rapid
changes in stream temperatures are required.
Example 4.5. Let us compare parallel-flow and counter-flow heat ex-
changers when the initial and final values of the temperature of the heat ex-
changing fluids are the same. Let us assume that the heating fluid has the initial
and final temperature 500 and 150qC. The heated fluid has the initial and final
temperature values 80 and 130qC (fig. 4.2). The logarithmic mean temperature
difference amounts to 180.2K in the case of a counter-flow and 131.4K in the
case of a parallel flow. Hence, the parallel-flow heat exchanger requires, in the
considered example, a heat transfer area 37% larger than the counter-flow heat
exchanger.
6. When choosing streams for a heat exchange, try to match streams
where the final temperature of one is close to the initial temperature of
the other.
This ensures that the maximum exergy is recovered in the heat exchange
process or the heat transfer area can be reduced.
Figure 4.2: Temperature distribution in a parallel-flow and counter-flow heat

exchanger.
Example 4.6. Let us consider a heat exchanger fed with hot combustion
gases and heating two streams of fluid. The final temperature of the first stream
is higher than the initial temperature of the second one (fig. 4.3a). To attain a
smaller distance between the mentioned temperatures, a common part of the heat
exchanger heating simultaneously both fluid streams can be realized (fig. 4.3b).
This solution is in accordance with the pinch method [34]. Considering the
temperature values cited in fig. 4.3, and assuming that the heat transfer coeffi-
cients are the same, the heat transfer area of the second version is smaller than
that of the first one. The ratio of the values of the heat transfer area is 0.91.
Example 4.7. Repowering of the conventional power plant fed with coal
may be attained by means of the primary gas turbine fuelled with natural gas.
Usually in the supplemented scheme the heat-recovery boiler of the gas turbine
is used to preheat the feed water of the conventional power plant. The initial re-
generative water preheaters fed with bleed steam are partially or totally swit-
ched off. However, the final temperature of the preheated water is considerably
lower than the initial temperature of the outlet gases flowing from the gas
turbine. Hence, in the hot part of the waste-heat boiler of the gas turbine the
exergy losses are large.
High temperature differences in the hot part of the waste heat boiler may
be reduced by introducing into this boiler not only water preheating but also
steam superheating [84], fig. 4.4. This solution improves the utilization of the
expensive natural gas and the efficiency of the total plant. Figure 4.5 presents the
distribution of temperature and exergy losses in the waste-heat boiler used for
the preheating of feed water and secondary superheating of steam.
Figure 4.3: Temperature distribution at simultaneous heating of two fluid streams.

Figure 4.4: Scheme of the combined power plant with the secondary steam
superheater shifted to the waste-heat boiler of the gas turbine.
Figure 4.5: Temperature distribution and exergy losses in the waste heat boiler
used for the preheating of feed water and secondary superheating of
steam.
7. The flow heat capacities of the streams exchanging heat should be

similar. If great differences appear, consider the partitioning of the
stream with a greater heat capacity between two or more heat ex-
changers heated (or cooled) with additional streams.
The exergy losses should be uniformly distributed within the heat exchanger.
Example 4.8. Let us consider a heat exchanger fed with hot combustion gases
and heating a fluid which has a stream with a heat capacity smaller than that of the
combustion gases (fig. 4.6). The required final temperature of the heated stream is
near the initial temperature of the combustion gases. However, the drop of the
temperature of combustion gases is smaller than the increase of the temperature of
the heated medium. Therefore, the outlet temperature of the combustion gases is
not sufficiently low, and their utilization degree is not satisfactory. This utilization
degree can be improved by reducing the flow rate of combustion gases and using
the remaining part for heating another medium. The mentioned reduction of the
flow rate at 21.4% would decrease the outlet temperature of combustion gases down
to 110qC. This would require, however, an increase of the heat transfer area in a
proportion of 1.56.
Figure 4.6: Temperature distribution when heating a stream with a small heat
capacity.
8. Minimize the use of intermediate heat transfer fluid while exchanging

heat between two streams.
The application of an intermediate fluid increases the total heat transfer area
or increases the total exergy loss. It might be sometimes justified because of
the local conditions or by the long distance transportation of heat.
Example 4.9. Figure 4.7 presents the temperature distribution in a system of
two heat exchangers heating the combustion air for the Cowper stove by means
of combustion gases. The lack of place within the duct of combustion gases
makes it impossible to apply an immediate heat transfer from the combustion
gases to the heated air. Therefore, an intermediate heat carrier with a high
volumetric heat capacity has been applied to transfer heat from the stream of
combustion gases to the combustion air.
In the considered case the total exergy loss remains unchanged after introducing
an intermediate heat carrier. However, the same heat stream will be transferred
twice, with a smaller temperature difference between the heating and the heated
medium. Therefore, the required increase of the total heat transfer area will be
considerable. Assuming the same heat transfer coefficient as by immediate heating,
we obtain a mean temperature difference twice smaller. The required total heat
transfer area will be four times larger. Usually the application of an intermediate
heat carrier with a higher volumetric heat capacity ensures an increase of the heat
transfer coefficient, but it cannot increase twice. If it increases, for example, 1.5
times, the total heat transfer area will increase 2.7 times in comparison with the
system operating without any intermediate heat carrier.
Figure 4.7: Application of an intermediate heat carrier in the heat exchanger.

Example 4.10. In a vapour-compression heat pump an intermediate heat

carrier is usually used between the bottom heat source and the evaporator [83]
(fig. 4.8). This leads to a lowering of the evaporation temperature, increasing
the compression work and some increase of useful heat. The value of COP
becomes lower. The quantity Tb in fig. 4.7 represents the temperature of the
bottom heat source, Tib the mean temperature of the intermediate heat fluid of
this cycle is represented by the area 1-2-3-5-1. After introducing the intermediate
heat carrier the cycle passes through the points 1c-2c-3-4c-1c, and the internal
driving work per unit of the working fluid is represented by the area 1c-2c-3-5c-1c.
The heat absorbed from the bottom heat source changes only slightly.
Let us assume the temperature of the bottom heat source (Tb = 8qC), the
mean temperature difference between the bottom source and the intermediate
heat carrier (Tic–Tb = 3K), between the evaporating fluid and the intermediate
heat carrier (Tib–Tev = 3K), the working fluid F22, the condensation temperature
(Tcn = 45qC), the internal adiabatic efficiency of the compressor 0.75. The
internal COP (without taking into account the mechanical efficiency of the
compressor and the electromechanical efficiency of the electric motor) amounts
to 5.25 with the consider ed intermediate heat carrier and 6.15 without this heat
carrier.
Figure 4.8: Influence of an intermediate heat carrier between the bottom heat
source and the evaporator of a heat pump.
9. Exergy losses due to the hydraulic friction or irreversible heat

transfer are the greater, the lower the temperature in the process is.
Minimize these losses especially below the ambient temperature.
The influence of hydraulic friction has been discussed in section 1.3. (fig.
1.2) presents the results of hydraulic friction during the adiabatic flow of
a fluid stream. Below the ambient temperature, in a chilling stream, the
absorption of friction heat reduces the amount of heat removed from the
process and thereby requires an increase of the refrigerant flow rate and
driving energy in the refrigerator. Synergistic negative effects appear.
10. Minimize the throttling of steam or other gases.
Throttling causes a destruction of exergy. The throttling exergy loss
increases as the volume becomes greater. Usually it does not have any
economic justification, but sometimes is unavoidable.
Example 4.11. Figure 4.9 presents the entropy increase due to the
throttling of working fluid in the vapour-compression Linde-cycle. It results
in a decrease Gqb of the amount of heat extracted from the bottom source.
Thus, it decreases the useful effect of a refrigerator or heat pump.
However, the efforts to eliminate this exergy loss have not given any
positive results. For example, the realization of the non-throttling periodically
operating Granryd-cycle introduces new exergy losses which can be greater
than the initial throttling loss [79].
Figure 4.9: Deleterious impact of the throtting in the Linde-cycle.

11. Fans or compressors should be located in the coolest place of the

process.
The driving power of compressors and fans is proportional to the volume,
and hence, decreases if the temperature drops. Figure 4.10 presents the
adiabatic enthalpy increase of the compressed gas or vapour. The higher the
initial temperature, the greater the required compression work is.
12. Eliminate leaks in pipelines, valves and combustion chambers.
Losses of compressed gases, losses of hot combustion gases or penetration
of excessive air into combustion gases ducts or combustion chambers leads
to a great decrease in the efficiency of the total system.
13. Remember that in systems driven with chemical, nuclear or mechanical
energy the rejection of heat to the environment in condensers of
turbines, refrigerators, etc. is a reflection of the irreversibilities within
the plant.
Decrease of the heat losses from condensers can be attained only by a
reduction of irreversibilities within the plant. The rejection of heat in
condensers cannot be eliminated by the recompression of vapour (for
example, in evaporator systems).
Figure 4.10: Adiabatic compression of a gas.

Example 4.11. Figure 4.11 presents a multistage evaporation plant. The first
stage is fed with steam (for example, from a heat-and-power plant). The steam
generated in this stage flows to the second stage and evokes an evaporation of
the liquid in this stage. A similar task is performed by the steam generated in this
stage. The steam from the last stage flows to the condenser.
Figure 4.12 presents a single-stage evaporator equipped with a compressor
of the steam generated inside the evaporator. The compressed steam delivers heat
to the evaporation process. Apparently this installation does not need any con-
denser. However, it is driven with electricity, usually delivered from a conden-
sation steam power plant. Hence, the condensation has not been eliminated, it is
only moved to another place.
14. Avoid the compression of steam which has been expanded previously.
In this case the exergy loss appears two times. Figure 4.13 presents an
adiabatic irreversible expansion of the steam and the subsequent adiabatic
irreversible compression. The work of compression is greater than that of
expansion. However, the recompression of the expanded steam has some-
times an economic justification.
Example 4.13. Let us consider the transportation of a counter-pressure steam
from the heat-and-power plant to the industrial consumer, which demands a large
stream of 0.4MPa steam and a small stream of 0.8MPa steam. It is possible to
produce two kinds of counter-pressure steam in the considered heat-and-power
plant, but it would be necessary to build two pipelines from the heat-and-power
plant to the industrial consumer. The investment expenditures can be reduced by
building only one pipeline for the 0.4MPa steam and to apply the recompression of
the necessary part of it within the plant of the consumer.
Figure 4.11: Multi-stage evaporator.

Figure 4.12: Single-stage evaporator with a vapour compression.
15. If you can reduce some exergy loss, try not to increase another exergy loss
appearing parallel.
Example 4.14. In heating systems equipped with a simple boiler, large exergy
losses appear inside the heated rooms due to the irreversible heat transfer between
the heating medium and the heated room. The introduction of a low-temperature
heating system (for example, a floor heating system) can reduce considerably the
exergy losses in this room, but increases the exergy losses in the boiler.
Example 4.15. The increase of the combustion temperature, for example, by
means of the preheating of combustion air, decreases the exergy losses con-
nected with the combustion, but increases the irreversibility of heat transfer
between the combustion gases and the heated agent.
Figure 4.13: Recompression of a previously expanded stream.

16. Avoid the elongation of the chain of thermodynamic processes.

Every new process introduces new exergy losses and additional investment
expenditures.
Example 4.16. The proposed schemes of the humid air turbine (HAT)
usually contain an aftercooler of the compressed air installed after the com-
pressor (for example [14]). It makes it possible to decrease the temperature of the
outlet gases discharged to the environment. However, the compressed air
flowing from the aftercooler is again heated in the regenerative preheater fed
with the working fluid from the turbine. Hence, the aftercooler elongates the
chain of processes, increases the investment expenditures and introduces addi-
tional exergy losses. Figure 4.14 presents a scheme of HAT with multi-point
water injection, blade cooling and aftercooler of the compressed air.
Szczygiel [90] compared the scheme with an aftercooler of the total stream
of the compressed air (fig. 4.14) with a scheme with a smaller aftercooler applied
only for cooling the stream of cooling air (fig. 4.15). The obtained results are
presented in table 4.1. The best efficiency values appear for the scheme with an
aftercooler applied only for decreasing the temperature of the cooling air.
Figure 4.14: Scheme of the humid air turbine with the aftercooler of the
compressed air CL, CH – low pressure and high pressure stage of
the compressor, T1}T4 — stages of the turbine, C1 —
intercooler and preheater of the injection water, C2 — external
intercooler, C3 — aftercooler, CC — combustion chamber,
H1}H3 — humidifiers of the compressed air, D1, D2 —
distributors of the cooling air, R, R1 — regenerative preheater of
air, W1,W2 — streams of the injection water, 1}12 — streams of
the working fluid.
Figure 4.15: Scheme of the humid air turbine with an aftercooler of the
compressed air applied only for cooling the stream of cooling air.
17. Try to introduce cogeneration processes producing simultaneously two

or more useful effects.
A cogeneration process (for example, the cogeneration of heat and
electricity) denotes a considerable shortening of the chain of processes and
therefore ensures a great reduction of exergy losses within the entire system.
18. Consider the influence of the proposed changes in energy management
on the exergy losses in other links of the system.
For example, the electrical heating of rooms results in an increase of the
exergy losses in the power plant. Remember also, that the separate
optimization of some link of energy systems is usually not exact because of
the mutual influence of particular processes taking place within the system.
Table 4.1: Influence of the aftercooler on the efficiency of the HAT power plant.
Temperature
after the Energy efficiency, %
turbine aftercooler applied only
qC without aftercooler with aftercooler to the cooling air
1200 47.67 45.35 47.88
1300 48.85 47.15 49.35
1400 49.82 48.57 50.69

19. Remember that the cost of exergy increases along the chain of processes.
For example, the cost of the fuel exergy in a power plant is smaller than the
production cost of the steam exergy, and the latter is smaller than the
production cost of electricity.
20. Try to reduce the exergy losses in places where they are the greatest,
and in places where they are most expensive.
Some of the 2nd Law inefficiencies cannot be avoided, others can.
Concentrate on those which can. For example, the losses of electricity in an
electrical grid are very undesirable.
Leites, Sama and Lior [33] published 12 directives resulting from the 2nd
law and pertaining to the chemical technology. Many of them are similar to the
above cited rules (for example to the rules 2, 3, 5, 7), however, some of them
may be especially important for chemical technological processes. For example,
the directive 4 is worth citing:
“If the reaction is exothermic, it should begin at the heightened temperature.
An endothermic reaction should begin at a lowered temperature. If the reaction
runs with an increase of volume, begin it at a heightened pressure. The reaction
running with decreasing volume should begin at a lowered pressure. The cited
rule is only apparently not conform with the law of le Chatelier”. The conditions
of the chemical reaction should not be favorable for the reaction rate because
every increase of this quantity denotes an increase of the rate of exergy loss.
Leites advises to begin the selection of the scheme of a technological process
from a quasistatic course, running through the equilibrium states, without any
exergy losses. So we can find indications how to select the real scheme burdened
with possibly minimum exergy losses.
Exercises
4.1. Calculate the minimum attainable increase of the heat transfer area due
to the introduction of the intermediate heat carrier. Assume that the heat transfer
coefficient between the intermediate heat carrier and the walls of the heat
exchangers is infinitely large. The resistance of heat conduction in the walls of
heat exchangers may be neglected. The heat transfer coefficients on the side of
the main heat carriers and their heat capacities are the same.
4.2. In a simple steam power plant the exergy efficiency values of its main
parts are: boiler 0.45, turboset 0.82, transformation and transmission system 0.9.
Assume that the flow rate of the chemical exergy of fuel amounts to 1000MW.
Calculate how the increase of exergy loss amounting to 10MW influences the
amount of electricity delivered to the consumer, if it appears, (1) in the boiler, (2)
in the transformation and transmission system.
Chapter 5
Depletion of non-renewable natural exergy

resources; thermo-ecological cost
5.1. Definition of the thermo-ecological cost
The inevitable depletion of non-renewable natural resources is very dangerous for

the future existence of mankind. Exergy can be accepted as a common quality
measure of all natural resources. Therefore, the cumulative exergy consumption of
non-renewable natural resources, termed ecological cost, has been proposed by
Szargut as a measure of their depletion [62, 65, 76, 77]. Recently the term thermo-
ecological cost has been introduced [80]. The set of eqns (3.6) can be used for the
calculation of thermo-ecological costs but the quantity Ej should comprise only non-
renewable resources. Additionally, the deleterious ecological impact of waste
products should be taken into account.
The thermo-ecological cost can be calculated in a global or regional scope. In
the second case the influence of the interregional exchange of goods should be
taken into consideration.
5.2. Evaluation of the thermo-ecological cost of the waste products
The waste products of every process usually exert a deleterious impact on the
environment. Three kinds of this impact can be named: the corrosion of buildings,
machines and equipment, the reduction of agricultural and forest production and
the damage in human health. The corrosion is most important All the mentioned
negative effects should be compensated by an additional consumption of useful
products substituting the destroyed useful products or preventing possible damage
[76]. The determination of the coefficients expressing the additional consumption
of useful products is very difficult. The assumption that ecological losses are
proportional to the exergy of waste products [2], is not justified. For example, CO
has a relatively great exergy, but does not cause any corrosion of useful products.
Therefore, Szargut [77] proposed to evaluate the deleterious impact of waste
products by means of their monetary index of harmfulness. The additional exergy
consumption of non-renewable natural resources due to the emission of waste

products (for example in kJ/kg) can be expressed as:
Bı k
ȟk (5.1)
DCP ¦ Pk ı k
k
where B = annual consumption of the non-renewable exergy from own sources of

the considered region
Vk = monetary index of harmfulness of the kth waste product
DCP = domestic consumption product.
Pk = annual emission of the kth waste product in the country.
The domestic consumption product (DCP) expresses the monetary value of

all useful final products used in the consumption sector, except those used in
production processes. Equation (5.1) takes into account the reduction of DCP
due to the emission of waste products (the last term in the denominator). The
values of the monetary index of harmfulness have been assessed by many
authors, and the obtained results differ considerably [20, 93, 107]. Usually
gaseous waste products have been analyzed: sulfur oxides, nitric oxides, CO,
benzo-a-pyrone. It is very difficult to determine the considered index for CO2
because its emission changes the composition and parameters of the natural
environment, evoking the greenhouse effect. It leads to climatic changes and to
a rise of the sea level. So far the evaluation of the monetary index of the harm-
fulness of CO2 is conventional and very low.
5.3. Balance equations
After introducing the coefficients [k the set of balance equations determining the
value of the specific thermo-ecological cost takes the form:
ȡ j ¦ ( f ij aij )ȡi ¦b ¦ p
sj kj ȟ k ¦ arj ȡ r (5.2)
i s k r
where Uj,Ui = specific thermo-ecological cost of the major product of the jth and
ith process
bsj = exergy consumption of the sth non-renewable natural resource, per
unit of the jth product
pkj = emission of the kth waste product per unit of the jth product
Ur = specific thermo-ecological cost of the imported rth semi-finished
product.
The thermo-ecological cost of the production of machines and installations
may be taken into account by means of the consumption coefficient aij from eqn
(3.9).
DEPLETION OF NON-RENEWABLE NATURAL EXERGY RESOURCES 93
The set of eqns (5.2) can be formulated separately for a group of production
processes having weak connections with the remaining part of the network of
production processes.
5.4. Influence of the interregional exchange
The thermo-ecological costs of particular products differ in various regions

because of differences in the applied technologies. The influence of the inter-
regional exchange should be taken into account when determining the indices
of thermo-ecological costs in the considered region.
In eqn (5.2) the thermo-ecological costs of imported goods can be replaced
by the equivalent thermo-ecological costs of exported goods [68]. The
financial means for the import are acquired by the export. Hence, the men-
tioned equivalence can be determined only by means of classical economic
indices. It can be assumed that the thermo-ecological costs of imported goods
related to a unit of monetary value is the same as that burdening the exported
goods.
The index of the thermo-ecological costs of exported goods per monetary
unit can be expressed as follows:
¦S ȡ
i
i i
ȡm . (5.3)
¦S D
i
i i
imported product is proportional to its monetary value Dr:
¦S ȡ
i
i i
ȡr ȡ m Dr Dr . (5.4)
¦S D
i
i i
Hence, the specific thermo-ecological costs of the rth imported product

depends on unknown values Ui of the thermo-ecological costs of the exported
domestic products.
The component of eqn (5.2) representing semi-finished products can be ex-
pressed as follows:
1
¦a rj ȡr ȡ m ¦ arj Dr ¦ȡ S ¦a i i rj Dr ¦ȡ di ij (5.5)
r r ¦ Si Dr
i
i r i
where:
¦a D
r
rj r
dij Si . (5.6)
¦S D
i
i i
All the quantities appearing on the right-hand side of eqn (5.6) are known.
Hence, the auxiliary coefficients dij are known, too, and can be introduced into the
set of eqns (5.2). The final form of eqn (5.2) is
ȡ j ¦ ( f ij aij dij )ȡi ¦b ¦ psj ȗ

kj k (5.7)
i s k
The thermo-ecological cost (global or regional) can be smaller than the

exergy when the considered product is burdened mainly with the consumption of
the renewable primary exergy (for example, agricultural products burdened with
the consumption of the renewable exergy of solar radiation or the electricity
produced from renewable resources). The regional thermo-ecological cost can be
smaller than the exergy also in the case when the considered region (for example,
Switzerland) exports mainly high-tech products fabricated with a small con-
sumption of domestic non-renewable exergy and imports energy carriers and
semi-finished products requiring a great consumption of non-renewable exergy.
Hence, interregional exchange can exert an essential influence on the regional
thermo-ecological costs.
The number of unknown quantities Ui appearing in the set of eqns (5.7) is
equal to the number of equations. However, the application of the set of eqns (5.7)
is not possible, if we want to perform the calculations in steps, as mentioned above
because in every one of eqns (5.7) the thermo-ecological cost of all the exported
goods does appear. Therefore, an iterative method has been proposed by Stanek
[54]. The exported goods should be divided into some groups of similar products.
For every group the thermo-ecological cost should be calculated by means of the
sequence method applying an iterative procedure. The first approximation can be
based upon the assumption that the thermo-ecological cost of the exported goods
Um per unit of their monetary value equals the mean thermo-ecological cost per
monetary unit of the domestic consumption product:
B
ȡr Dr ȡ m Dr (5.8)
DCP
The values Ur resulting from eqn (5.8) should be used in the sequence
calculation method of the particular groups of the exported goods. The obtained
results should be introduced into eqns (5.3) and (5.4) to correct the values of Ur.
These values can be used to correct the values of the mean products taken into
account in the balance eqns (5.2). These corrected values can again be used in
the sequence calculation of the thermo-ecological cost of exported goods.
5.5. Calculation of the thermo-ecological cost
In order to calculate the domestic thermo-ecological cost, its values for the dele-
terious waste products should be determined. According to eqn (5.1) the first step of
the calculations is the determination of the annual consumption of non-renewable
exergy. The second step comprises the application of the set of balance eqns (5.7) to
the main strongly connected products. In the third step the sequence method can be
applied for weakly connected products.
Example 5.1. The annual exergy consumption of domestic non-renewable

natural resources in Poland contains the exergy Bhc of hard coal, Bbc of brown coal,
Bng of own natural gas, Bcr of own crude oil, BS of sulfur and BCu of copper ore.
According to Stanek [53] in 1997 the mentioned values were:
B Bhc Bbc Bng Bcr BS BCu

3608 u 10 638 u 10 140 u 109 13 u 109 33 u 109 15 u 109
9 9
4445 u 109 MJ/a
The domestic consumption product was 143.1×109 $/year. The thermo-

ecological cost per unit of DCP was 31.1 MJ/$.
Example 5.2. The annual emission of the main waste products (SO2, NOx and
dust) amounted in Poland in 1997 to:
PSO2 2181 u 103 , PNOx 1141 u 103 , Pd 1130 u 103 t/a.
The following monetary indices of harmfulness have been accepted:
ıSO2 1500, ı NOx 1500, ıp 310 $/ t.
The indices of thermo-ecological cost of waste products, resulting from eqn (5.1)
are:
ȟ SO2 45, ȟ NOx 45, ȟp 9.3 MJ/kg.
Example 5.3. Determining the specific thermo-ecological cost of principal

products burdened with a large consumption of non-renewable exergy, a system
containing the following plants has been taken into account [53]: coal mines,
natural-gas wells, a thermal power plant, a coking plant, an iron-ore sinter plant and
a blast-furnace plant. The system consumes imported iron ore and natural gas. The
major products of the considered system are as follows:
1 - hard coal used in power plants,

2 - hard coal used in the coke production and injected into the blast furnace,
3 - natural gas (domestic and imported),
4 - electricity,
5 - coke,
6 - iron ore sinter,
7 - pig iron,
8 - imported iron ore.
The fabrication of the mentioned products is connected, but slightly, with other
branches of industry. The consumption of steel in the mining of coal has been
substituted by the consumption of pig iron. It has been assumed that coke-oven
gas substitutes (with the substitution efficiency equal to one) the imported natural
gas (which closes the balance of demand), the basic production of blast-furnace gas
substitutes (with an efficiency of 0.7) the imported natural gas, and the peak
production of this gas substitutes the hard coal used for the production of elec-
tricity. The consumption of the energy carrier for the transportation of the con-
sidered products has been taken into account. The influence of the injection of
various auxiliary fuels (replacing partially coke) has been examined (coke-oven
gas, natural gas and pulverized coal).
The first step of approximation is presented in the considered example. The
thermo-ecological cost of imported materials has been estimated by means of eqn
(5.8). From this equation it results that Um = 34.4 MJ/$. The inaccuracy of this
estimation does not influence much the calculated values of the thermo-ecological
cost of domestic products. The thermo-ecological cost of imported iron ore (1.032
MJ/kg) results from its cost (30 $/t).
The following balance equations have been formulated for the calculation of
the thermo-ecological cost:
Extraction and delivery of coal. The balance equations have the same form for
both kinds of coal. Only the specific exergy is different:
(1 a11 )ȡ1 Ȥ 3 a31ȡ3 a41ȡ 4 a71ȡ 7 b1 (1 Ȥ 3 )a31ȡ3r ¦ pk 1ȟ k ,

k
(5.9)
(1 a22 )ȡ 2 Ȥ 3 a32 ȡ3 a42 ȡ 4 a72 ȡ 7 b2 (1 Ȥ 3 )a32 ȡ3r ¦ pk 2 ȟ k ,
k
where F3 = fraction of domestic natural gas in the total consumption

U3r = specific thermo-ecological cost of the imported natural gas.
The following coefficients have been introduced:
a11 a22 0.0058 kg/kg, (ȡ1 ,ȡ 2 MJ kg)

a31 a32 0.000041 kg/kg, (ȡ3 MJ kmol),
a41 a42 0.175 MJ/MJ, (ȡ 4 MJ MJ),
a71 a72 0.004 kg/kg, (ȡ 2 MJ kg),
p1 p p2 p p1SO2 p2SO2 p1NOx p2NOx 0.0001 kg/kg,
b1 21.8, b2 30.25 MJ/kg.
Extraction and delivery of domestic natural gas:
ȡ3 a43ȡ 4 b3 (5.10)
where: a43 4.17 MJ/kmol, b3 802 MJ/kmol
Production and delivery of electricity:
(1 a44 )ȡ 4 a14 ȡ1 ¦p k
4k ȟk (5.11)
where:
a44 0, a14 0.156 kg/MJ,

p4SO2 0.00218, p4NOx 0.00101, p4 p 0.00347 kg/MJ.
Production of coke:
ȡ5 a25ȡ 2 a45ȡ 4 ¦p
k
5k ȟ k (a35 f35 )ȡ3r (5.12)
with:
a25 1.6 kg/kg, a35 ak 5 [( MH L ) k ( MH L )5 ]v3 k 0.00458 kmol ng/kg,

f 35 f k 5 [( MH L ) k ( MH L )5 ]Q 3 k 0.0112 kmol ng/kg, a45 0.0958 kg/kg,
p5SO2 0.000129, p5NOx 0.000473, p5 p 0.000613 kg/kg.
where ak5, fk5 = coefficient of the consumption and by-production of coke-oven

gas
(MHL)k,(MHL)3 = lower heating value of coke-oven and natural gas, MJ/kmol
Q3–k = energy efficiency of the replacement of natural gas by coke-
oven gas.
Production of iron ore sinter:
ȡ6 a46 ȡ 4 a56 ȡ5 ¦p k
6k ȟ k a86 ȡ8 r a36 ȡ3r (5.13)
with the values:
a86 0.827 kg/kg, a36 ak 6 [( MH L )k ( MH L )5 ]v3 k aw6 [( MH L ) w ( MH L )3 ]v3 w

0.0002247 kmol/kg, a46 0.1073 MJ/kg, a56 0.0612 kg/kg,
ȡ8 r 6.6 MJ/kg,
p6SO2 0.003, p6NO x 0.0005, p6 p 0.006 kg/kg.
where aw6, Q3–w = coefficient of the consumption of blast-furnace gas and the energy
efficiency of the replacement of natural gas by blast-furnace gas
(MHL)w = lower heating value of blast furnace gas, MJ/kmol.
Production of pig iron (together with the production of blast, steam for blast
humidification and oxygen). The by-production of electricity appears in the gas
turbine (expansion of blast-furnace gas) and in the counter-pressure steam turbine
delivering steam for blast humidification. The injected natural gas has been parti-
tioned into the domestic and imported part [by means of the coefficient F3 from
eqn (5.9)]:
ȡ 7 (a17 f17 )ȡ1 a27 ȡ 2 Ȥ 3 a37 ȡ3 (a47 f 47 )ȡ 4 a57 ȡ5 a67 ȡ 6

(5.14)
¦p
k
7k ȟ k [(1 Ȥ 3 )a37 a37c f 37c ]ȡ3 r
The specific consumption of the first kind of coal (used for the production of
electricity):
a17 D (1 ȗ D )(a1D O 2 D a1t X D a1 X ) (5.15)
where D = consumption of dry blast per pig iron unit

]D = coefficient of blast losses in Cowper stoves
O2D, XD = consumption of technical oxygen and humidifying steam per unit
of dry blast
a1D, a1t, a1X = specific consumption of coal (first kind) for blast compression, for
the production of oxygen and for the production of humidifying
steam.
The coefficient of the by-production of coal (first kind) results from the by-
production of the peak part of blast-furnace gas (used in the boiler house):
( MH L ) w
f17 (1 Į w ) f w7 Ȟ1 w (5.16)
H L1
where fw7 = coefficient of the by-production of blast furnace gas, kmol/kg pig iron
HL1 = lower heating value of coal, MJ/kg
Dw = fraction of the basic part of the produced blast-furnace gas
Q1–w = energy efficiency of the replacement of coal by peak blast-furnace
gas.
The basic part of blast-furnace gas replaces imported natural gas:
( MH L ) w
f 37c Į w f w7 Q3 w (5.17)
( MH L )3
where Q3–w = energy efficiency of the replacement of natural gas by blast-furnace

gas.
The coefficient a27 of the consumption of the second kind of coal results
from its injection into the blast furnace. The consumption of coke-oven gas
injected into the blast furnace is expressed in units of the replaced imported
natural gas:
( MH L ) k
a37c ak 7 Ȟ 3 k (5.18)
( MH L )3
where ak7 = coefficient of the consumption of the injected coke-oven gas.

The by-production of electricity results from the expansion of blast-furnace
gas ftr7 and from cogeneration with the production of steam for humidification of
the blast:
f 47 f tr 7 D(1 ȗ D ) X D eX (5.19)
where eX = by-production of electricity per unit of back-pressure steam.

The coefficients of consumption ai7 and by-production fi7 depend on the
operational parameters applied in the blast-furnace process:
ai 7 f ( F , TD , O 2D , X D , pG ), fi 7 F( F , TD , O 2D , X D , pG ) (5.20)
where TD = temperature of the preheated blast

PG = pressure at the top of the blast furnace.
Relations (5.20) have been determined by means of the balances of
elements and energy [53]. The mean values of the emission indices of waste
products have been assumed:
p7SO2 0.182, p7 NO x 0.042, p7 d 0.367 kg/Mg pig iron.
The calculation results are presented in table 5.1. They should be corrected
after an iterative determination of the thermo-ecological cost of the imported
natural gas. The mutual connections between the considered pro-cesses result
in a dependence of the values of the thermo-ecological cost of the remaining
products (except pig iron) on the parameters of the blast-furnace process.
However, this influence is very small. The thermo-ecological cost of the pig
iron has been calculated with the following operational parameters: thermal
parameters of the blast TD = 1100oC, O2D = 24%, pressure of the top gas pG =
0.3MPa, auxiliary fuel (pulverized coal) consumption 3GJ/(Mg pig iron).
Table 5.1: Exemplary values of the thermo-ecological cost.
Material or energy Thermo-ecological cost

Coal for power plants 1.12 HL
Coal for coking plants 1.11 HL
Natural gas (domestic) 815 MJ/kmol
Electricity from coal 3.13 MJ/MJ
Coke 49.6 MJ/kg
Iron ore sinter 4.5 MJ/kg
Pig iron (liquid) 32.2 MJ/kg
Example 5.4. In order to determine the values of the domestic thermo-

ecological cost of imported fuels (natural gas and crude oil), the thermo-ecological
cost of exported goods should be calculated. This problem has been solved by
Stanek [54] using an iterative procedure.
Table 5.2 contains after [54] data concerning the structure of the Polish do-
mestic products exported in 1997. Table 5.3 presents the results of iterative cal-
culations. In table 5.3 the thermo-ecological cost of exported machinery and devices
is expressed in MJ/$.
Table 5.2: Structure of the export of domestic products from Poland in 1997 [54].
Amount Monetary Thermo-ecological

per year value per cost per
Branch 106 kg/year year monetary unit,
number Name and unit $/year 106 $/year MJ/$
1 Coke, kg 3234 273 542.6
2 Coal, kg 29 500 1124.5 711.8
3,4 Steel blocks, kg 1124 243.3 195.6
5 Sulfur, kg 1127.4 48.5 571.9
6 Copper, kg 361.6 346 383.5
7 Cement, kg 2827 113.8 148.1
8 Steel products, kg 2935 1128 146.1
9 Aluminium, kg 111.9 302.7 92.5
10 Machines and devices, $ 1268.6 1268.6 13.9
11 Agricultural prod. (meat), kg 444.8 643 17.5
12 Agricult. prod. (vegetal), kg 979.2 647.3 15.5

Table 5.3: Iterative calculation of the thermo-ecological cost of exported goods,

MJ/kg (No 10* in MJ/$) [54].
Iteration
Branch 0 1 2 3
1 49.61 45.85 45.77 45.77
2 27.10 27.13 27.13 27.13
3 39.34 44.54 44.64 44.64
4 35.18 38.95 39.07 39.02
5 24.59 24.60 24.60 24.60
6 369.5 366.97 366.92 366.92
7 6.95 5.96 5.96 5.96
8 49.42 56.10 56.23 56.23
9 249.36 249.62 249.63 249.63
10* 13.00 13.09 13.92 13.92
11 13.92 25.26 25.48 25.48
12 5.59 10.19 10.27 10.27
In the last column of table 5.2 the values of the thermo-ecological cost of the
exported products are cited. Most advantageous, from the point of view of the
depletion of domestic natural resources is the export of machinery and food. Most
disadvantageous is the export of raw materials and fuels, particularly coal. The
results of iterative calculations of the thermo-ecological cost of imported fuels are
presented in table 5.4 [54].
Table 5.4: Thermo-ecological cost of the imported fuels [54].
Thermo-ecological cost Imported Imported

Iterative per monetary unit crude oil natural gas
step MJ/$ MJ/kg MJ/kmol
0 31.13 6.85 95.89

1 218.1 47.9 671.7
2 221.7 48.7 682.8
3 221.8 48.8 683.0
4 221.8 48.8 683.0
The domestic thermo-ecological cost of imported fuels depends on the

structure of the export. This dependence has been presented in table 5.5 after
Stanek [54]. The smaller the ecological cost of the exported product per mone-
tary unit, the smaller is the thermo-ecological cost of imported fuels.
5.6. Sustainability index

The ratio of the thermo-ecological cost to the exergy characterizes the fraction of the
non-renewable exergy in the fabrication process of the considered useful product.
Usually its value is greater than 1. For some products fabricated with a large parti-
cipation of the renewable exergy we can obtain values smaller than 1 (for example,
for forest or agricultural products, for electricity from wind- or water power sta-
tions). The development of human economy should result in a reduction of the
discussed index. Its value smaller than 1 is desirable as a condition of sustainable
development. Therefore, the name sustainability index has been proposed for the
thermo-ecological cost to exergy ratio [5]:
ȡ
rB (5.21)
b
In table 5.6 some exemplary values of the sustainability index have been
presented. The indices for industrial products result from the calculations of Stanek
[54]. To compare the industrial products with the agricultural ones, two values have
been determined according to Learch [32]. When considering the production of
corn, the thermo-ecological cost is smaller than the exergy of the product since this
product is generated mainly from the exergy of solar radiation. However, further
Table 5.5: Influence of the structure of export on the thermo-ecological cost of
imported natural gas [54].
Thermo-ecological Thermo-ecological
cost per monetary cost of natural gas Ratio
Variant of structure unit of export, MJ/$ MJ/kmol U/b
Structure of export similar to 31.1 95.9 0.12
that of production
Structure of export similar to 31.1 95.9 0.12

that of production
Structure of export 221.8 683.1 0.85

corresponding with table 5.2.
Export based on coal 711.8 2192 2.7
Export based on machinery 13.9 42.8 0.05
Export based on agricultural 16.6 51.1 0.06

productss
Table 5.6: Sustainability index of some industrial and agricultural products.
Thermo-ecological Sustainability
Material or energy kind cost index
Coal for power plants 22.6 MJ/kg 1.037
Coal for coke production 31.1 MJ/kg 1.028
Natural gas (domestic) 815 MJ/kmol 1.016
Natural gas (imported) 683 MJ/kmol 0.85
Crude oil (imported) 48.8 MJ/kg 1.07
Electricity 3.13 MJ/MJ 3.13
Coke 49.6 MJ/kg 1.554
Pig iron* 32.2 MJ/kg 3.68
Corn 4.2 MJ/kg 0.35
Flour 22 MJ/kg 1.75
Meat 26 MJ/kg 2.50
(*) See table 5.1.
processing uses mainly non-renewable exergy, and just after the second step (the
production of flour) the thermo-ecological cost becomes greater than the exergy
of the product. The value for meat [54] results from mean statistical data con-
cerning the energy consumption in the meat industry.
Exercises
5.1. Calculate the sustainability index characterizing the production of heat

by means of the heat pump considered in exercises 2.15 and 3.2.
5.2. Calculate the sustainability index characterizing the production of heat
by means of a compressor heat pump extracting the bottom heat from the ground
and compare this heat pump with that absorbing the bottom heat from the atmos-
pheric air. The mean temperature of the ground is 8qC. The mean air tempe-
rature during the heating season is 2qC. The working fluid is freon R22. Its
evaporation temperature is 6qC (for heat absorption from the ground) and 0qC
(heat absorption from the atmospheric air). The condensation temperature is
45qC. The internal isentropic efficiency of the compressor is 0.8, the electro-
mechanical efficiency of a complex compressor-electrical motor is 0.75. The
heat of mechanical and electrical losses does not flow to the heated room. The
tempe-rature of the heated room is 20qC. The influence of the consumption of
materials used for the construction of the heat pump may be neglected. The
cumulative efficiency of electricity delivery is 0.31. Electricity is produced by

means of non-renewable fuels.
5.3. Calculate the thermo-ecological cost and sustainability index characterizing
the production of heat by means of a solar collector. Assume that the mean yearly
thermal power of the collector is 100 W/m2. The temperature of the preheated heat
carrier is 40qC and of the return carrier 25qC. The consumption of materials per 1
m2 of the collector area is: copper tubes and plate 27 kg/m2, steel 20 kg/m2, glass 10
kg/m2. The recovery coefficient of metallic scrap, eqn (3.9) is: copper 0.5, steel 0.3.
The thermo-ecological cost of glass is 33.4 MJ/kg. The amount of glycol filling the
system is 20 kg/m2, its specific chemical exergy amounts to 19450 kJ/kg, and CExE
= 0.72. The life time of the collector is 15 years. The annual mean ambient tem-
perature is 8qC.
5.4. Calculate the thermo-ecological cost and sustainability index characteriz-
ing the production of electricity in a wind power plant. The annual utilization time
of the nominal power is 2000 h/year, the steel consumption per 1 MW of nominal
power is 240 t/MW, the life time is 15 years, the utilization efficiency of the steel
scrap (after the wear of the installation) is 0.35. The efficiency of electricity trans-
formation and transmission 0.9.
5.5. Compare the thermo-ecological cost of electricity produced in Poland in a
power plant fed with hard coal and imported natural gas. The energy efficiency of
the power plant is 0.38 for hard coal and 0.37 for natural gas. The cumulative
exergy efficiency of coal delivery 0.93. The efficiency of the transformation and
transmission of electricity is the same in both cases and amounts to 0.9. According
to table 5.4 the thermo-ecological cost of imported natural gas is 683 MJ/kmol. Its
lower heating value is 778 MJ/kmol. The thermo-ecological cost of the production
equipment may be neglected.
Chapter 6
Economic applications of exergy

6.1. Exergo-economics
Exergy losses appearing in particular links of the analyzed system are not all
of the same importance. In the course of thermodynamic processes the specific
economic value of exergy increases. For example, in a steam power plant the
specific economic value of fuel exergy is smaller than that of live steam, and the
latter one is smaller than the specific economic value of the produced electricity.
Hence, exergy losses are more harmful, the farther the analyzed link is located in
the chain of partial processes.
The cited statement stimulated many authors to propose economic applica-
tions of exergy called thermoeconomics, exergo-economics or exergonomics [18,
28, 29, 94–96, 98]. However, exergy is a thermo-dynamic concept, not an
economic one [61].
An interesting variant of exergo-economics elaborated by Tsatsaronis and
his coworkers [95] aims at the determination of the costs of exergy losses appea-
ring in particular links of the considered system. The comparison of the calcu-
lated costs can indicate the links which should be improved. The sum of the costs
of exergy losses can be used as an objective function when optimizing the design
and operational parameters (which should be performed using the iterative
method).
Two methods of optimization of production processes can be applied: the
method of the minimization of production costs or the method of minimiza-
tion of the cost of exergy losses. The first method is usually applied. A scien-
tifically correct determination method of the cost of exergy losses is difficult, it
should be based on the comparison of costs of a real process and a reversible
process.
Tsatsaronis does not apply the mentioned comparison. He uses the equa-
tions of exergy balance and of costs balance. He differentiates the components
representing the ‘fuel’ and those representing the useful product. For example,
when analyzing an adiabatic steam turbine the exergy of fuel is expressed by
means of the difference of the exergy B1 of the delivered steam and exergy of
the outlet steam B2. The performed mechanical work W is the useful product.
The cost of the produced work Cw results from the balance of costs:
Cw B1c1 B2 c2 R (a)
where c1, c2 = specific cost of exergy of the components of ‘fuel’,

R = component of costs resulting from the investment expenditures.
The cited author maintains that from the costs balance results the equality
c1 c2 (b)
However, the equality (b) is purely conventional, because the outlet “fuel com-
ponent” differs in parameters and quality from the inlet “fuel component”.
The exergy balance of the real and reversible process has a form:
B1 B2 W įB, B1s B2 s W (c)
where W = the performed work

GB = sum of exergy losses in the considered process (together with external
losses if they exist).
The index s indicates the quantities appearing in the reversible process.
The balance of costs of a comparative reversible process may be expressed
in the form:
Cws B1s c1 B2 s c2 s Rs (d)
Assuming:
c2 c2 s c1 , R Rs (e)
and taking into account the difference of exergy balances (c) we obtain after
subtracting eqns (a) and (d) the economic loss Cirr due to the irreversibility of the
considered process:
Cirr Cw Cws įBc1 (6.1)
Equation (6.1) results from the convention (e). However, despite the for-
mulated critical remarks, the method of Tsatsaronis is worth consideration and
application, because it makes it possible to evaluate approximately and compare
the economic onerosity of exergy losses appearing in particular links of the
considered system.
Other variants of thermo-economy assume that the specific cost of exergy is
the same for all the useful products of a cogeneration process. This assumption
is used at the partitioning of production costs between the useful products
appearing simultaneously in the same point of the considered system. The cited
ECONOMIC APPLICATIONS OF EXERGY 107
assumption is also purely conventional. It does not take into account the
influence of the co-generation process on the economic effects of the total
system of energy and technological processes of the state.
The partitioning of the production costs between the useful products appear-
ing simultaneously in the same point of the system can be made by means of
purely economic tools, that is using the principle of avoided expenditures [81].
In every cogeneration process a major product can be distinguished. Its demand
determines the location of the plant and the production rate. The additionally
fabricated product can be called a by-product if it substitutes a major product
of another specialized process. The production cost of the by-product can be
determined according to the production costs avoided in the substituted spe-
cialized process. Thus, the principle of avoided expenditures takes into account
the influence of the co-generation process on the total energo-technological
system.
The principle of avoided expenditures can also be used to determine the
consumption of the driving exergy burdening the fabrication of the major pro-
duct of a cogeneration (combined) process:
1 § bb ·
b fm
Gm ¨© B f Gb Ș ¸¹ (6.2)
Bs
where bfm = specific consumption of the driving exergy burdening the major
product
Gm,Gb = amount of the major product and by-product
Bf = overall consumption of driving exergy
bb = specific exergy of the by-product
KBs = exergy efficiency of the avoided process of separate fabrication of
the by product.
Some authors propose a minimization of the entropy generation in the
considered link of the system, as a method of determining the optimum opera-
tional and construction parameters [4]. However, entropy is generated not only
in the considered link of the system, but also in the preceding links producing
semi-finished products and energy carriers supplied to the considered link [78].
When the considered process produces also waste products rejected to the
environment (external exergy losses), the entropy generation connected with the
considered process appears also in the environment. Hence, the minimization of
entropy generation does not ensure any minimization of cumulative exergy
losses connected with the considered process. It is additionally worth stressing
that even the minimization of cumulative exergy losses is not always expedient.
If the considered process is supplied with renewable energy carriers, the
objective function for the optimization should not contain the exergy losses
(entropy generation) connected with the utilization of renewable exergy. For
example, when optimizing the solar collector it would not be reasonable to take
into account the entropy generation connected with the absorption of solar
radiation because the destruction of exergy of solar radiation is not connected

with any economic or environmental losses.
6.2. Optimization of the thermo-ecological cost
The thermo-ecological cost may be accepted as an objective function when

optimizing the operational and construction parameters of some installation. The
objective function should contain the operational component comprising the
thermo-ecological cost of raw materials, semi-finished products and energy
carriers supplied to the investigated process and the investment component
comprising the thermoecological cost of the applied machines and installations.
According to the proof presented in chapter 3.2 the thermo-ecological cost of
human work should not be introduced into the objective function.
A considerable reduction of the depletion of non-renewable resources may
be attained by the secondary utilization of the materials remaining after the wear
and dismantling of the installation [15, 16]. This effect can be expressed by
means of the recovery factor um taking into account the fraction zs of the initial
amount of the mth material which can be used as a secondary raw material and
the ratio of the specific thermo-ecological cost Us of the substituted raw material
to the initial thermo-ecological cost of the mth material:
ȡs
um zs (6.3)
ȡm
When the investigated process produces one useful major product and some
useful by-products, and the required production capacity is given, the objective
function expressing the depletion of non-renewable exergy, and related to 1 year
has the form taking into account the principle of avoided expenditures and the
thermo-ecological cost of the products replaced by the useful by-products of the
investigated process [86]:
§ ·
PA Ĳn ¨
¨© ¦ G ȡ ¦ P ȟ ¦ G ȡ s
j
j j
k
k k
u
u i iu ¸
¸¹
(6.4)
1ª º
«
Ĳ «¬ ¦ G ȡ 1 u ¦
m
m m m
r
Gr ȡ r »
»¼
where G j ,ȡ j = nominal flow rate and specific thermo-ecological cost of the jth
raw material, semi-finished product or energy carrier supplied
to the production process
Pk , ȟ k = nominal flow rate and index of the specific thermo-ecological
cost of the kth deleterious waste product rejected to the en-
vironment
G u = nominal production rate of the useful uth by-product

UiSiu = specific thermo-ecological cost of the ith major product replaced
by the uth by-product and the replacement ratio in units of the ith
replaced product per unit of the uth by-product
Wn = annual operation time with nominal capacity
W = nominal life time of the installation, years
um = expected recovery factor of the mth material, eqn (6.2)
Gm,Um = consumption and specific thermo-ecological cost of the mth
material or energy carrier used for the construction of the
installation
Gr,Ur = expected consumption and specific thermo-ecological cost of the
rth material or energy carrier used in repairs.
Example 6.1. The optimization of the pipe diameter of a heat exchanger [86].
A tubular heat exchanger is considered. The consumption of heating fluid
(for example, steam), its temperature, the flow rate of heated water per one pipe,
the initial and final temperature of the heated water are given. The internal
diameter of the pipe is to be optimized. The decrease in this diameter increases
the flow velocity of heated water, and so decreases the heat transfer resistance
(hence, the heat transfer area), but increases the flow resistance (hence, the con-
sumption of electricity driving the water pump). The resistance of the heat con-
duction in the pipe wall can be neglected. A constant heat transfer resistance on
the external surface of the considered pipe can be assumed. According to eqn
(6.4) the objective function can be formulated as follows:
§ įp · 1
PA Ĳ n ¨ G s ȡ s Vw ȡel ¸ ¬ª ʌLDtȖ st ȡ st 1 ust ȡ P ¼º (6.5)
© ȘP ¹ Ĳ
where G s ,ȡ s = nominal flow rate and specific thermo-ecological cost of the

heating steam
Vw , įp = volumetric flow rate and pressure loss of the heated water
KP = efficiency of the complex: water pump with driving electric
motor
Uel = specific thermo-ecological cost of electricity
L,D,t = length, internal diameter and wall thickness of the considered
pipe
Jst,Ust = mass density and specific thermo-ecological cost of the steel
pipe
UP = thermo-ecological cost of the pump.
The thermo-ecological cost of the heating steam is constant and can be omitted
in the objective function. A constant value of the thermo-ecological cost of the
pump may also be accepted. Introducing additionally the known heating power Q
one can obtain:
įp 1 Qt
PA Ĳ nVw ȡel Ȗ st ȡ st (1 ust ) (6.6)
ȘP Ĳ Į'Tm
where 'Tm = the mean temperature difference between the heating and heated
fluid
D = convective heat-transfer coefficient on the internal surface of the
considered pipe.
The pressure loss of the heated water can be expressed as follows:
L w2 8Vw2 Q 8V 2
įp Ȝf Ȗw Ȝ f LȖ w Ȝf Ȗ w 3 w6 (6.7)
D 2 ʌ 2 D5 Į'Tm ʌ D
where Of = coefficient of hydraulic friction
D = internal diameter of the considered pipe
w = flow velocity of water
Jw = mass density of water.
Additionally, the following expressions are introduced:
4Vw Ȗ w Ȝw
D , Ȝf 0.046 Re 0.2 , Į 0.023Re0.8 Pr 0.4 (6.8)
ʌ Re Șw D
where KwOw = dynamic viscosity coefficient and thermal conductivity of water.

The following formula expresses the operational component of the annual
thermo-ecological cost, where the quantity Re represents the decision variable:
Ĳ n ȡel Q 0.154 Ș5w Re 4
PAop (6.9)
Ș P 'Tm Ȝ w Pr 0.4
Ȗ 4wVw2
In order to develop a similar formula for the investment component of the

thermo-ecological cost, a linear dependence between the thickness of the pipe
wall and its internal diameter has been assumed:
4Vw Ȗ w
t t0 aD t0 a (6.10)
ʌ Re Șw
The investment component has the form

Ȗ st ȡ st (1 ust ) Q 55.4Vw Ȗ w § 4Vw Ȗ w ·
PAinv 0.4 ¨ t0 a ʌȘ Re ¸ (6.11)
Ĳ 'Tm Ȝ w Pr Șw Re1.8 © w ¹
The form of eqns (6.9) and (6.11) indicates that the result of optimization
does not depend on the value of the expression Q ( 'Tm Ȝ w Pr 0.4 ) . The
introduction of these quantities into the calculations makes it possible to
determine only the annual thermo-ecological cost of the considered device.
The following data have been accepted for exemplary calculations:
Wn = 4200 h/year, W = 10 years, Uel = 3.15, KP = 0.7, Ust = 60 MJ/kg, ust = 0.35,
Jst = 7800 kg/m3, Vw = 0.0005 m3/s, Jw = 1000 kg/m3, Ow = 0.68 W/(m K),
Pr = 1.7, Kw = 2.8u10–4 Ns/m2, Q = 30 kW, 'Tm = 40 K, t0 = 0.001 m,
a = 0.075.
After introducing these data eqns (6.9) and (6.11) take the form:
5.97 u108 § 170.5·

PAop 6.45 u1023 Re4 GJ/a, PAinv ¨ 0.001 ¸ GJ/a (6.12)
Re1.8 © Re ¹
where the quantity 0.001 + 170.5/Re expresses the thickness of the pipe wall.
The calculation results are presented in fig. 6.1. The optimum internal
diameter of the pipe results from the optimum value of Re, according to eqn
(6.10):
Reopt 80000 Dopt 0.0284 m
The optimum flow velocity of the heated water is 1.27 m/s.
Figure 6.1: Determination of the optimum internal diameter

of the pipe of a water preheater.
Example 6.2. Optimization of a shell-and-tube water preheater [86].

A tubular water heater with a once-through flow of water has been
considered. The stream of water and its initial and final temperature are given.
Saturated steam with a given temperature is the heating medium. When analy-
zing this heat exchanger two decision variables should be optimized, for ex-
ample, the number of tubes (or water stream per one tube) and the internal
diameter of the tubes (or the internal Reynolds number).
The following data have been accepted for exemplary calculations:
Q = 600 kW, Vwt = 0.005 m3/s, ust = 0.5, W = 15 years, t0 = 0.0015 m.
The remaining data are the same as in the Example 6.1.

The investment component of the objective function should be supplemented
in comparison with (6.11) because the consumption of steel should take into
account not only the tubes but also the remaining parts of the heat exchanger.
Additionally, the consumption of electricity for the mechanical working and
welding of the parts of the heat exchanger should be introduced into the
objective function. The constant part of the mentioned components of the object-
ive function may be omitted. It can be assumed that the diameter of the shell is
proportional to the diameter of the tubes and to the square root of the number of
tubes. The mass of the shell is additionally proportional to the length of the
tubes. Hence, the changing part of the mass of the remaining parts of the heat
exchanger (except the tubes) may be presented as follows:
Gstc țD n (1 ȤL) (6.13)
where N,F = coefficients resulting from the design of heat exchangers.

Similarly, the changing part of the consumption of electricity for the
mechanical working and welding of the parts of the heat exchanger should be
divided into two components, one proportional to the total perimeter of the cross-
section of the tubes, (hence, to the product nD), and the second one to the
diameter of the shell (hence, to the product D n ):
§ Ȟ ·
Eel ȝDn ȞD n Dn ¨ ȝ ¸ (6.14)
© n¹
where P,Q = coefficients of proportionality.

The following coefficients of proportionality have been accepted:
ț 700 kg/m Ȝ = 0.15 l/m, ȝ = 0.08 GJ/m, Ȟ 0.3GJ/m.
The form of eqns (6.13), (6.14) and the values of the coefficients of pro-
portionality depend on the type of the heat exchanger.
The pressure loss of the heated water should take into account the flow
resistance inside the pipes and the local resistance at the inlet and outlet of the
tubes. It has been assumed that the sum of local resistances equals the dynamic
pressure of the water stream inside the pipes:
1 § L ·
įp Ȗww2 ¨ Ȝ f 1¸ (6.15)
2 © D ¹
where Of = coefficient of hydraulic friction

L, D = length and internal diameter of the considered pipe
w = flow velocity of water
The following formula expresses the operational component of the annual
thermo-ecological cost, where the quantity Re represents the decision variable:
WnUel 2 4 ª Q 0.154Kw5 Kw4 º

PAop n Re « 0.4 2 4
0.308 » (6.16)
KP ¬« 'TmOw Pr Vwt J w VwtJ w3 ¼»
The investment part has a more complicated form:
Ust 1 ust ª 55.4QV J J

wt w st
§ 4aVwt J w ·
PA inv « 0.4
t
1.8 ¨ 0 ¸
W «¬ 'TmOwKw Pr Re © SKw n Re ¹
4NVwt J w § 13.85OQ ·º (6.17)

¨1 0.4 0.8 ¸
»
SKw n Re © 'TmOw Pr Re ¹ »¼
Uel 4Vwt J w § Q ·
P
W SKwRe ¨© n ¸¹
After introducing the given data, eqns (6.16) and (6.17) take the form:
PAop 3.868 u1023 n2Re4 GJ/a (6.18)
2.754 u1011 § 1706· 3.18 u104 § 3.7 u104 ·

PAinv ¨ 0.0015 ¸ ¨1 ¸
n Re1.8 © n Re ¹ n Re © n Re0.8 ¹ (6.19)
48 § 30 · GJ
¨8 ¸
Re © n¹ a
Calculations may be performed for some values of the number of tubes. For
every assumed value of n, the local optimum value of Re can be determined.
After that the optimum values of two decision variables may be selected. The
calculation results are presented in table 6.1.
The optimum values can be accepted as follows:
nopt = 25, Reopt = 48 000, Dopt = 0.019 m, Lopt = 1.78 m, wopt = 0.711 m/s,
Dopt = 5686 W/(m2 K), Vw = 0.0002 m3/s.
Table 6.1: Optimization of a shell-and-tube water preheater.
PA op PA inv PA op + PA inv
n Re GJ/year GJ/year GJ/year
22 40 000 0.0479 0.6476 0.6955
50 000 0.1170 0.4739 0.5909
60 000 0.2426 0.3717 0.6143
24 40 000 0.0570 0.4271 0.4841
48 000 0.1183 0.3199 0.4332
50 000 0.1392 0.2949 0.4341
25 40 000 0.0619 0.4017 0.4707
48 000 0.1283 0.3024 0.4307
50 000 0.1511 0.2830 0.4341
26 40 000 0.0669 0.3918 0.4587
50 000 0.1634 0.2725 0.4359
60 000 0.3389 0.2059 0.5448
27 40 000 0.0722 0.3766 0.4488
50 000 0.1762 0.2629 0.4391
60 000 0.3654 0.1992 0.5646
6.3. Optimization of the exergetic cost

According to the opinion of Sciubba [49, 50] the optimization of the operational
and construction parameters should be performed by means of a quantity
containing not only the cumulative consumption of exergy of all the consumed
materials and energy carriers, but also the cumulative consumption of exergy
burdening the human work. In the present book the quantity introduced by
Sciubba has been named exergetic cost.
The mean exergetic cost of human work should result from the ratio of the
total consumption of non-renewable exergy in the considered country to the total
amount of work-hours. The total exergy cost of the human work should be equal
to the total consumption of non-renewable exergy. If the optimization comprises
only the exergy cost of human work (immediate or embodied), the results should
be similar to that of classical economic optimization because in both cases the
main task of the optimization would be the economy of human work.
The optimization of the thermo-ecological cost (determined without any
thermo-ecological cost of human work and demonstrated in the previous para-
graph) ensures the economy of non-renewable exergy resources. In this case the
total exergetic cost of all the consumed materials should also equal the total
consumption of non-renewable exergy. Hence, the optimization of the exergetic
cost leads to a result representing some compromise between the economy of
human work and the economy of non-renewable exergy resources.
6.4. Correction of the economic optimization
Sometimes the economic analysis does not take into account the influence of the
parameters of an energy carrier on its quality. Such an inaccuracy can be corrected
by means of the exergy analysis. For example, the heat lost from the pipeline of live
steam in a steam power plant has a better quality, than the mean quality of heat
delivered inside the boiler. The economic value of the lost heat is higher than its
mean value. It can be approximately evaluated by means of exergy:
T T0 Tm
k km (6.20)
T Tm T0
where km,k = mean specific cost of the heat delivered inside the boiler and local
specific cost of the heat lost from the pipeline
Tm,T = mean temperature during the absorption of heat inside the boiler,
and local temperature in the pipeline.
After this correction the calculated optimal thickness of the thermal insu-
lation of the pipeline increases.
6.5. Influence of the thermodynamic imperfection on the

investment cost
The improvement of the exergy efficiency of some thermal installation requires

an increase of investment expenditures. However, the higher the exergy effi-
ciency of the selected solution, the larger additional investment expenditures are
required to improve the installation. The investment cost becomes infinitely
large, if the required exergy efficiency amounts to 100%. Therefore, after
Szargut and Maczek [63] an approximate equation can be formulated expressing
the dependence between the exergy efficiency KB and the rated exergy capacity
B of single-purpose installations:
m
J § ȘB ·
J0 Bj (6.21)
0¨
© 1 ȘB ¸¹
where J0 = constant component of the investment cost

j0 = factor of investment cost increment per unit of exergy capacity
m = exponent related to the type of installation.
The annual operational cost of the installation can be expressed as follows:
§k ·
K BĲn ¨ B K¸ K0 (6.22)
© ȘB ¹
where Wn = annual time of operation with a rated capacity

kB = unit cost of driving exergy
ki = unit cost of service, maintenance, and renovation

K0 = constant component of the annual operational cost.
The total annual cost of the production of the required annual useful exergy
effect is
KA İJ K (6.23)
where H denotes the annual capital recovery factor (factor of fixed costs).
The exergy efficiency is a sole decision variable in eqn (6.22). The optimum
value of this efficiency, ensuring a minimum annual production cost, is ex-
pressed as follows:
1
ȘBopt (6.24)
1 (mL)1/(m1)
where:
İj0
L (6.25)
kB Ĳn
is the dimensionless number of thermoeconomic similarity.

The presented equations do not take into account the technical limitations
that can arise in the design of the installation.
6.6. Evaluation of the natural mineral capital and the freshwater

resources of the Earth
6.6.1. Natural mineral capital of the Earth
Valero and his co-workers have undertaken an attempt to evaluate the mineral
capital of the Earth in the area of the production of the most important metals
[99, 100]. They considered 42 elements, mainly metals. The mineral capital has
been defined as the economy of the consumption of primary exergy which can
be attained thanks to the extraction and utilization of natural resources whose
useful components are more concentrated than in the reference environment or
appear in the form of chemical compounds with positive chemical exergy (for
example in the form of sulfides). Hence, the quantity determining the mineral
capital contains two components, the concentration component and the chemical
component.
The concentration component of the mineral capital results from the
difference of the cumulative consumption of the primary exergy which is
necessary to extract the useful component from the reference environment and
from the mined mineral. In both cases the final concentration of the useful
component should equal the value required for further metallurgical treatment.
The approximate evaluation is based upon the assumption of ideal solutions.
The equations formulated in the present book differ from those of Valero et
al. A scheme of the separation of the mined material is presented in fig. 6.2. To
obtain raw material prepared for metallurgical treatment, containing 1 mol of the
useful component with its molar concentration yr, the amount of the mineral
extracted from the mine should be 1/y1 (where y1 is the molar fraction of the
useful component in the mined mineral), and the obtained amount of the raw
material will be 1/yr.
The minimum work necessary to perform the separation presented in fig. 6.2
(assuming that the considered materials have the properties of an ideal solution)
may be expressed as follows:
ª y 1 yr 1 yr § 1 1 · 1 º
W1 RT0 «ln r ln ¨ ¸ ln » (6.26)
«¬ y1 yr 1 y1 © y1 yr ¹ 1 y1 »¼
The minimum work W2 necessary to separate the metallurgical raw material

from the reference environment (with the molar fraction y0 of the useful
component) should be calculated under the assumption that this separation does
not influence the composition of the environment (thanks to the considerably
larger mass of the environment):
§ y 1 yr 1 yr ·
W2 RT0 ¨ ln r ln (6.27)
© y0 yr 1 y0 ¸¹
The difference W2–W1 expresses the theoretical economy of exergy

attainable thanks to the use of natural resources which have a larger
concentration of the useful component in comparison to the reference
environment. The real economy, characterizing the natural mineral capital,
should additionally take into account the cumulative exergy efficiency Ș s of the
separation process:
ni ni ª y 1 y0 1 1 º
BNCi (W2 W1) RT0 «ln 1 ln(1 y0 ) ln(1 y1)» (6.28)
ns ns ¬ 0y 1 y1 yr y1 ¼
where ni denotes the amount of the mol of the ith component in natural
resources of this component.
Figure 6.2: Scheme of the separation of the mined mineral u — useful

component, w — waste component.
The second term in square brackets of eqn (6.28) has usually a very small
value.
Example 6.4. In the case of producing iron, the compound Fe2O3 has been
assumed as a useful component of natural resources. The minimum economic
exploitable concentration has been assumed as y1 = 0.5. The molar fraction in
the reference environment is y0 = 0.0068. The concentration required for
metallurgical treatment is yr = 0.7. According to Valero et al [99] the world
reserves of Fe2O3 in iron ores are 74u109 ton (4.63u1011 kmol). The cumulative
exergy efficiency of separation is ns 0.03 (assuming the immediate efficiency
0.1 and cumulative efficiency of driving exergy production 0.3). From eqn (6.28)
the concentration part of the mineral capital of iron-rich minerals is
BNCFe2O3 6.95 u 109 GJ 5500 Mtoe.
Valero et al [99] calculated the value 10,164 Mtoe. They estimated the total
concentration component of the natural capital to be 22,000 Mtoe (about 15% of
the proven oil reserves).
According to Valero et al [100] the concentration component of the annual
consumption of the mineral capital is highest for iron ores (51.5%, 140
Mtoe/year), followed by phosphorus (11.6%), copper (8.3%), sodium (5.7%),
zirconium (5.8%), aluminium (5.6%) and magnesium (5.1%).
Natural resources applied for the production of metals sometimes have a
high positive chemical exergy. Most important are sulfides. The consumption of
exergy for the production of metal from sulfide can be smaller than in the case of
production from oxides. Valero et al estimated the average attainable economy
of exergy: about 80 GJ/ton metal. The natural mineral capital of the reserves
of sulfides resulting from their chemical composition is about 1250 Mtoe,
considerably less than the concentration component.
6.6.2. Resources of fresh water
Valero et al [101] determined also the resources of the exergy of fresh water.
This evaluation bases upon the statement that the chemical and potential exergies
of seawater equal zero. Two components of the resources of fresh water have
been considered: the stationary resources contained in nature (in subterranean
reservoirs, lakes, rivers and ice sheets), and the renewable resources generated by
the evaporation of liquid water from the ocean and continents surface. The
evaluated stationary resources of fresh water (about 2.5% of total resources) are
35u1018 kg (about 69% in the ice sheet and 30% in subterranean reservoirs).
According to the example 2.8 (p. 46) the total rate of evaporated water is 15u109
kg/s. Valero cites a slightly different value 18u109 kg/s. The evaporated water
returns to the Earth’s surface in form of rain and snowfalls. However, only about
23% of them reach the surface of continents. Hence, the generation rate of
renewable fresh water resources is about 3.45u109 kg/s. If the stationary
resources had to replace the natural generation of fresh water, they would be
exhausted in about 300 years.
The minimum desalination exergy (minimum consumption of exergy for the
separation of fresh water from the seawater) results from eqn (2.12a). According
to the data from table 2.2, the average molarity of salt in seawater is 0.474
mol/kg H2O. Hence, the molar fraction of salt is 0.00854. From (2.12a) at T0 =
298K it results that bdes = 1.18 kJ/kg H2O. From the cited rate of precipitations
reaching the surface of continents results the rate of the renewable chemical
exergy of fresh water: 4.1 TW. This is near the rate of the potential energy of all
rivers taken together (cited in example 2.8).
Valero [101] cites the values of practical consumption of exergy in de-
salination processes. From comparison with the above cited chemical exergy
result the following values of exergy efficiency of desalination processes:
multistage evaporative installation 0.39%

inverse osmosis 2.7%
heat and power plant with evaporator 0.59–0.72%.
Exercise
6.1. Calculate the optimum thickness of a thermal insulation of the external

wall of a house from the point of view of the economy of non-renewable exergy
resources. The insulation layer consists of polystyrene foam with the thermal
conductivity 0.04 W/(m K) and density 20 kg/m3. The initial heat transfer
coefficient is 1.3 W/(m2 K). The internal temperature is 20qC. The mean am-
bient temperature in the heating season is 2qC, the duration of the heating season
5400 h/year. The thermo-ecological cost of heat is 1.32 J/Jth. The thermo-
ecological cost of polystyrene production is 165 MJ/kg. The lifetime of the
insulation layer is 20 years.
Chapter 7
Application of exergy for determining the

pro-ecological tax
7.1. Necessity of a new tax
The income tax imposed in all countries represents some kind of penalty for the
positive effects of human activity (effective work, invention etc.). Only VAT (the
value added tax) burdens the consumption, but the height of VAT is established
arbitrarily by the state administration. Therefore, some authors proposed to intro-
duce taxes imposed for the negative effects of human activity, like the deleterious
impact on the natural environment.
Slesser [51] proposed to introduce a new environmentally sensitive concept
in taxation. The new tax, named unitax, should replace VAT. According to this
concept the unitax should be imposed on primary energy sources where they enter
the economy. This denotes a considerable increase in the price of primary and trans-
formed energy. Slesser does not use exergy. His concept does not give any possi-
bility of taking into account the harmful effects of the environmental pollution
because this pollution does not appear at the level of gathering the primary energy.
Wall [105], Gong and Wall [23] proposed to apply the use of exergy of non-
renewable resources together with the exergy of waste products released to the
environment as a base for an internationally governed tax. The income from this tax
should support the research and other activities improving the exergy efficiency and
the use exergy. Hence, Wall proposed an exergy-based tax as an auxiliary mean,
supplementing the actual taxes. He has not formulated any equations determining
the cumulative depletion of non-renewable natural exergy resources.
Repetto, Dover et al [46] propose that the tax should rather be imposed for
negative effects, like pollution, waste generation, congestion. The shift of taxes
from the positive to negative effects of human activity by the introduction of a
pollution charge should ensure not only ecological but also general economic profits
because it should enhance a more rational use of natural resources and a better
protection of the environment. According to Repetto et al [46], the shift of 1 US$
from the positive zone to the negative one can bring an economic profit of as much
as 0.45–0.8 US$. Hence, these authors proposed to substitute entirely the existing
tax by a new pro-ecological pollution tax. Von Weizsäcker et al [102] write that the
pollution tax could permit to attain a doubled well-being, at a twice lowered
consumption of resources. Tsatsaronis [96] proposes to introduce a worldwide
taxation agreement imposed on the use of electricity and fossil fuels to enhance the
use of renewable resources.
Environmental damages are not the sole and most important negative result
of human activity. The depletion of non-renewable natural resources can be
even more dangerous for the future of humankind [62]. Wall [103] proposed to
apply exergy as a general measure of the quality of natural resources. Szargut
[62, 80] introduced the concept of thermo-ecological cost expressing the
cumulative consumption of non-renewable primary exergy, appearing in all the
links of the energo-technological system as a result of the fabrication of some
considered final product.
Szargut [62] stressed the necessity to minimize the thermo-ecological cost.
An important tool of this minimization can be a pro-ecological tax substituting
the actual taxes. It should be proportional to the cumulative depletion of non-
renewable natural resources [85]. In the first step, the existing VAT could be
substituted by an objective, non-arbitrary pro-ecological tax. In the second step
also the personal income tax might be substituted.
7.2. Structure of the pro-ecological tax
In many countries a tax burdening the consumption of goods and services, called
VAT is applied. However, the height of this tax is arbitrary; it depends on the
decision of the state administration. The proposed pro-ecological tax could be
very similar to VAT, but should be proportional to the thermo-ecological cost
(cumulative consumption of non-renewable primary exergy), and should
substitute the VAT-tax being in force. The personal income tax could also be
eliminated after introducing the pro-ecological tax, according to the principle
that the tax should be imposed only for negative results of human activity.
The index of proportionality between the pro-ecological tax and the thermo-
ecological cost should depend on the total consumption of non-renewable ex-
ergy in the considered country. This quantity may be determined by means of
statistical data. For example, after Stanek [53] the total consumption of re-
newable exergy in 1995 amounted in Poland to 4122 PJ. This value takes into
account hard coal (3314.7 PJ), lignite (579.2 PJ), domestic natural gas (144.6
PJ), copper ore (15.2 PJ), sulfur (46.2 PJ) and domestic crude oil (22.1 PJ).
The mentioned coefficient of proportionality should be expressed in
monetary units per unit of exergy. The value of the coefficient may depend on
the state policy. It should take into account the demand for financial means for
investments, social needs, education, military needs, police, administration, etc.
The drop of the coefficient would denote an approval of the increase of
consumption.
APPLICATION OF EXERGY FOR DETERMINING THE PRO-COLOGICAL TAX 123
The explained principle needs some correction, if the pro-ecological tax

should take into account also the harmful impact of waste products. To avoid
a double counting, the coefficient of proportionality x might be lowered. The
thermo-ecological costs of waste products should be added to the total con-
sumption of the non-renewable exergy:
x
¦Ȥ (7.1)
B¦Pȟ k k
k
where x = coefficient for the calculation of the pro-ecological tax

¦ Ȥ = the sum of all the tax values acquired by the state administration
B = annual domestic consumption of non-renewable exergy
Pk,[k = see eqn (5.1).
The coefficient x should be corrected every year according to the rate of
inflation, and to changes in the denominator of eqn (7.1). Changes of state
expenditures should also be taken into account.
Example 7.1. In 1997 the sum of the values of VAT amounted in Poland to
11.25u109 US$/year, and the sum of personal income tax to 9.10u109 US$/year.
The value of the quantity in the denominator of eqn (7.1) is
B ¦ Pk ȟ k 4455 u 109 174 u 109 4629 u 109 MJ/a

k
From eqn (7.1) it results that x = 0.0044 US$/MJ.

Example 7.2. According to Stanek [53], in 1997 the thermo-ecological cost
of electricity in Poland was 3.13 MJ/MJ. The pro-ecological tax per unit of
electricity would be 0.0141 US$/MJ= 0.0495 US$/kWh.
The thermo-ecological cost of the domestic natural gas was 815 MJ/kmol.
The ecological tax imposed on the domestic natural gas would be 3.59 US$/kmol
= 0.160 US$/mn3 (m3 in normal conditions).
Equation (7.1) can be explained by means of a simplified example. Assume
that hard coal is the only non-renewable resource consumed by two plants only.
The first of them burdens the environment with an amount Ps of deleterious
waste products, the specific thermo-ecological cost of which is [s. The second
plant does not produce any harmful waste products. Assume that the
consumption of semi-finished products and energy carriers in coal mines can be
neglected. According to eqn (7.1) the proportionality coefficient determining the
pro-ecological tax can be expressed as:
Ȥ1 Ȥ 2
x (7.2)
Bc Ps ȟ s
where F1, F2 = tax burdening the first and second plant,

Bc = exergy of the consumed coal.
The tax burdening the first and second consumer is
Ȥ1 ( Bc1 Ps ȟ s ) x, Ȥ 2 Bc 2 x (7.3)
The sum of the thus determined values of the tax satisfies eqn (7.2). A double
burdening of ecological losses with the tax has been avoided.
The structure of the pro-ecological tax may be similar to that of VAT. The
sale price of every product should be burdened with a tax resulting from the
values burdening the input components used in the last production link and
with a tax resulting from the thermo-ecological cost of the waste products of the
last link. Every intermediate producer should receive a refund of the tax after
he has sold his product. So the total value of the tax would be paid by the final
consumer. The calculation of the thermo-ecological cost would not be necessary
because the subsequent values of the tax would be calculated by the producers to
receive the refund of the tax. The calculation of the refunded tax may be based
on a balance equation similar to eqn (5.2) determining the thermo-ecological
cost:
§ ·
Ȥ j ¦ f uj Ȥ u ¦a Ȥ ¦a
ij i rj Ȥ r ¨ ¦ bsj ¦ pkj ȟ k ¸ x (7.4)
u i r © s k ¹
where aij, arj = consumption coefficient of the ith domestic and rth imported
semi-finished product or energy carrier per unit of the jth major
product together with the by-products,
fuj = coefficient of the by-production of the uth product per unit of the
jth major product,
bsj = coefficient of the immediate exergy consumption of the sth non-
renewable resource per unit of the jth major product, together
with the by-products,
Fi, Fu = pro-ecological tax burdening the jth major product and uth by-
product,
Fi, Fr = pro-ecological tax burdening the consumed domestic and im-
ported semi-finished products and energy carriers,
x = pro-ecological tax burdening the consumption of a unit of pri-
mary non-renewable exergy, eqn (7.1),
Pkj = amount of the kth aggressive component of the waste products
rejected to the environment per unit of the jth major product.
Equation (7.4) does not contain only the tax burdening the jth major product
but also the tax burdening the by-products. The product belongs to the by-products
if it replaces the major product of another specialized process. Therefore, the pro-
ecological tax burdening the by-product may be calculated by means of the

replacement ratio and the tax burdening the ith replaced major product, eqn (3.7):
Ȥu siu Ȥ i , f ui f ij siu (7.5)
where the replacement ratio siu expresses the number of units of the replaced
product per unit of the uth by-product. The replacement ratio should be deter-
mined by a qualified regulation office.
The correctness of the calculation results depends on the proper treatment of
the mines extracting non-renewable materials from natural deposits. The exergy
of these materials should be carefully determined. Any mine (of coal, crude oil,
natural gas, mineral raw materials) should pay the tax immediately after the ex-
traction, and receive the refund together with the tax burdening the bought
materials and the energy carriers.
It might be most difficult to determine the tax burdening the waste products.
Even if some partially conventional values of the monetary coefficients of harm-
fulness have been accepted and eqn (7.1) has been applied, additionally all the
production installations should be equipped with monitoring instruments deter-
mining the deleterious emissions. The correction resulting from deleterious
emissions is not very large, and therefore only the biggest production plants
should have monitoring equipment. For small producers the component of tax
taking into account deleterious emissions might be assumed conventionally
(depending, for example, on the kind and consumption of the used fuel and on
the kind of the applied technology).
7.3. Pro-ecological tax resulting from the use of machines and

installations
The pro-ecological tax burdening the purchase of machines and installations

results from the procedure of determining this tax. This tax should be added to
the sale price and reimbursed to the producer of the machines and installations.
The purchaser using these machines and installations in his production pro-
cesses should burden the price of his products with a respective fraction of the
mentioned tax. Calculating this fraction, the degree of the utilization of machines
and installations in the production process and their durability should be taken
into account. The fraction of the tax burdening the ith machine or installation per
unit of the jth product can be calculated as follows:
mij
aij (7.6)
s jGj
where mij = number of ith machines or installations to be used in the planned

period of the fabrication of the jth product
sj = planned period of production of the jth product in years
Gj = annual production of the jth product
The application of eqn (7.6) has an important disadvantage. The producer

buying the production machine or installation pays the discussed tax imme-
diately at the moment of purchase because it is contained in the price of the
machine or installation. So the producer grants some kind of loan to the state,
and the reimbursement will last some years in the form of an additional com-
ponent of the price of his products. Therefore, a discount calculus should be
applied. It can be done by means of the correction of the thermo-ecological cost of
the production machine, or more simply by the correction of the coefficient aij in
eqn (7.6). The discounted coefficient aijd, calculated without taking into account the
rate of inflation, may be expressed as follows:
mij r sjr
aijd aij (7.7)
Gj 1 1
1 s
1 s
(1 r ) j (1 r ) j
where r = annual rate of the discount.

The component of the pro-ecological tax added to the selling price of the jth
product to refund the tax Fi paid when purchasing the production installation,
calculated without inflation may be expressed as follows:
Ȥ id Ȥ i aijd (7.8)
The discounted coefficient is higher than the not-discounted. When the value
mij is not an integer, one of the machines is not worn after the finished period of
production, the producer cannot get back the total initially paid tax included into
the selling price of the product, but can sell the partially worn machine and so
get back the remaining part of the initial tax.
Example 7.3. Let us assume r = 0.08, s = 15 years. The ratio of the
discounted and not discounted coefficient is
aijd
1.752.
aij
The value resulting from eqn (7.8) should be actualized every year according to
the rate of inflation:
Ȥ in (1 in 1 )Ȥ i , n 1 (7.9)
where: n = order number of the year of operation of the production installation,

in–1 = annual rate of inflation in the preceding year.
7.4. Burdening of imports and exports
The pro-ecological tax burdening the exported products might be refunded to the
exporter similarly as in the case of other intermediate producers and should not
be added to the export price. On the other hand, it should be taken into account
that exported products burden the domestic economy with some depletion of the
resources of non-renewable exergy, but the financial means obtained from this
export make it possible to import some necessary foreign products. Therefore,
the imported products might be burdened with such a pro-ecological tax which
can compensate the tax refunded to the exporters. The calculation can be per-
formed by means of the monetary value of the export assuming that the monetary
unit of import should be burdened with a pro-ecological tax equal to that deter-
mined for the monetary unit of export. The following formula resulting from this
principle determines the pro-ecological tax burdening the imported products:
Ȥi Di
¦Ȥ e
(7.10)
E
where Fi = pro-ecological tax burdening the unit of the ith imported product
Di = monetary value of the unit of the ith imported product
¦ Ȥ e = sum of the values of pro-ecological tax, calculated for the exported
products and refunded to the exporters
E = monetary value of the annual export.
Example 7.4. After Stanek [54] in 1997 in Poland the mean thermo-
ecological cost per unit of the monetary value of the exported goods amounted to
220.3 MJ/US$. Thus, the pro-ecological tax per unit of the price of imported
goods would be 0.97 US$/US$.
The price of imported natural gas was 0.1 US$/ m3n . The pro-ecological tax
burdening the imported gas would be 0.0976 US$/ m3n , hence, less than for
domestic natural gas.
When the monetary value of the import is greater than the value of the
export, from eqn (7.4) results the sum of the values of the pro-ecological tax
greater than the sum refunded to the exporters. Such an effect can enhance the
export and lead to a reduction of the import.
7.5. Discussion
The introduction of the pro-ecological tax would not mean any increase in the
total sum of taxes. Only the distribution of taxes would be changed. The intro-
duction of the discussed taxes would stimulate the limitation of the use of
products burdened with a large consumption of non-renewable resources and
enhance the introduction of new technologies based upon renewable resources.
Therefore, it would stimulate new investments and decrease unemployment.
The proposed tax could reduce the consumption of less necessary products.
It is worth stressing that actually the economic conjuncture is realized by an
enhancement of the consumption. Such an economic policy is short-sighted
because it leads to an acceleration of the depletion of scarce non-renewable
natural resources of the Earth.
Exercises
7.1. Calculate the pro-ecological tax which should be added to the selling
price of electricity produced in a wind power plant. Assume the thermo-
ecological cost of the equipment of the wind power plant 12000 MJ/kW. The
annual time of utilization of the nominal power is 2000 h/year, the life time 15
years, the transformation and transmission efficiency of electricity 0.9. The
annual rate of discount is 0.08, the rate of pro-ecological tax per unit of the
thermo-ecological cost is 0.0044 US$/MJ. Assume that the financial indices
relate to the first year of operation. The consumption of materials for the
maintenance may be neglected.
price of heat produced in a water boiler fed with hard coal. The energy efficiency
of the boiler is 0.85. The thermo-ecological cost of the boiler may be neglected.
Take the rate of the pro-ecological tax per unit of the thermo-ecological cost
from exercise 7.1. The thermo-ecological cost of coal per unit of its heating
value take from table 5.1.
price of heat produced in a compressor heat pump with the energy index COP =
3.5. The thermo-ecological cost of electricity take from table 5.1. The thermo-
ecological cost of the heat pump installation per unit of thermal power is 15
GJ/kW. The life time of the installation is 20 years, the annual time of utiliza-
tion of the nominal power is 3500 h, the annual rate of discount is 0.08. Take the
rate of the pro-ecological tax per unit of the thermo-ecological cost from ex-
ercise 7.1.
7.4. Calculate the total reduction of the pro-ecological tax attained thanks to
the application of an additional layer of the thermal insulation to the external
wall of a house. The thickness of the additional insulation is 0.2 m. Take the
parameters characterizing the additional insulation, the conditions of heating and
the values of the specific thermo-ecological cost from Exercise 6.1., and the rate
of the specific pro-ecological tax from Exercise 7.1. The calculation result
should include the total life time of the insulation, relate to 1 m2 of the area of the
wall and be discounted to the first year after introducing the new insulation layer.
Appendix 1
Table I: Enthalpy of devaluation and standard chemical exergy of pure

substances, Tn = 298.15 K, pn = 101.325 kPa
Standard
Molecular Enthalpy of chemical
mass devaluation exergy
Substance State M Dn, kJ/mol bch n, kJ/mol
1 2 3 4 5
Al s 26.9815 930.69 795.7
Al4C3 s 143.959 694.51 4217.4
AlCl3 s 133.3405 467.18 352.2
Al2O3 s, D corundum 101.9612 185.69 15.0
Al2O3·H2O s, boermite 119.9765 128.35 9.4
Al2O3·3H2O s, gibbsite 156.0072 24.13 24.1
Al2S3 s 150.155 3313.81 2705.3
Al2(SO4)3 s 342.148 596.8 344.3
Al2SiO5 s, andalusite 162.046 28.03 9.2
Al2SiO5 s, kyanite 162.046 25.94 12.9
Al2SiO5 s, sillimanite 162.046 0 15.3
Al2SiO5·(OH)4 s, kaolinite 258.1615 68.25 12.0
3Al2O3·2SiO2 mullite 426.0536 630.11 63.2
Ba s, II 137.34 747.77 775.1

BaCO3 s, II 197.35 75.18 53.7
BaCl2 s 208.25 48.69 88.7
BaO s 153.34 194.15 252.0
BaO2 s 169.34 113.38 196.7
Ba(OH)2 s 171.36 45.93 160.3
BaS s 169.4 1012.88 929.0
BaSO4 s, barite 233.4 0 30.7
C s, graphite 12.01115 393.509 410.26

C s, diamond 12.01115 395.406 413.16
CCl4 l 153.823 578.95 473.1

substances, Tn = 298.15 K, pn = 101.325 kPa (continued)
Standard
1 2 3 4 5
C2N2 g, cyanogen 52.0357 1096.14 1118.9
CH4 g, methane 16.04303 802.3 831.6
C2H6 g, ethane 30.0701 1427.8 1495.8
C3H8 g, propane 44.0972 2045.4 2154.0
C4H10 g, n-butane 58.1243 2658.4 2805.8
C5H12 g, n-pentane 72.1514 3274.4 3463.3
C2H4 g, ethylene 28.0542 1323.1 1361.1
C3H6 g, propylene 42.0813 1927.7 2003.9
C2H2 g, acetylene 26.0382 1255.6 1265.8
C6H6 g, benzene 78.1147 3171.6 3303.6
C6H6 l, benzene 78.1147 3137.7 3298.5
C7H8 l, methylbenzene 92.1418 3736.4 3931.0
C8H10 l, ethylbenzene 106.1689 4347.7 4587.9
C10H8 s, naphtalene 128.1753 4984.2 5255.0
C14H10 s, anthracene 178.2358 6850.9 7218.1
CH2O2 l, formic acid 46.0259 213.0 291.7
C2H6O l, ethylalcohol 46.0695 1235.9 1357.7
C2H4O2 l, acetic acid 60.0529 786.6 908.0
C3H6O l, acethone 58.0807 1659.6 1798.5
C6H6O s, phenol 94.1141 2925.9 3128.5
C2H2O4 s, oxalic acid 90.0358 202.7 368.7
CH4ON2 s, urea 60.0558 544.7 689.0
CO g 28.0105 282.984 275.1
CO2 g 44.0095 0 19.87
CS2 l 76.139 2934.09 1694.7
Ca s, II 40.08 813.57 712.4

CaC2 s 64.1 1541.18 1468.3
CaCO3 s, aragonite 100.09 0 1.0
CaCO3·MgCO3 s, dolomite 184.411 0 15.1
CaCl2 s 110.99 178.21 87.9
CaFe2O4 s 215.77 161.07 104.0
Ca2Fe2O4 s 271.85 321.00 194.7
Ca2Mg5Si8O22(OH)2 s, tremolite 812.41 425.49 78.9
Ca(NO3)2 s 164.0898 –124.90 –81.4
CaO s 56.08 178.44 110.2
CaO·Al2O3 s 158.04 351.66 122.7
CaO·2Al2O3 s 260.00 541.71 138.4
3CaO·Al2O3 s 270.2 716.72 381.4
APPENDIX 131

Standard
1 2 3 4 5
12CaO·7Al2O3 s 1386.68 3415.71 1542.0
CaO·Al2O3·SiO2 s, anortite 222.038 273.92 65.6
Ca(OH)2 s 74.09 69.04 53.7
Ca3(PO4)2 s, D 310.18 0 19.4
CaS s 72.14 1056.57 844.6
CaSO4 s, anhydrite 136.14 104.88 8.2
CaSO4·½H2O s, D 145.15 83.16 12.1
CaSO4·2H2O s, gypsum 172.17 0 8.6
CaSiO3 s, volastonite 116.16 90.24 23.6
Ca2SiO4 s, E 172.24 232.28 95.7
Ca3SiO5 s 282.32 424.94 219.8
Cd s, D 112.4 357.1 293.8

Cd s, Q 112.4 356.51 293.2
CdCO3 s 172.41 0 40.6
CdCl2 s 183.31 126.04 73.4
CdO s 128.4 98.95 67.3
Cd(OH)2 s 146.41 38,26 59.5
CdS s 144.46 920.6 746.9
CdSO4 s 208.46 149.24 88.6
CdSO4·H2O s 226.48 84.79 80.6
Cl2 g 70.906 160.44 123.6

Cl g 35.453 201.9 87.1
Cr s 51.996 569.86 584.7

Cr3C2 s 180.01 2415.85 2493.0
Cr7C3 s 400.005 5007.63 5156.7
CrCl2 s 122.902 361.91 352.2
CrCl3 s 158.355 281.05 301.9
Cr2O3 s 151.99 0 117.2
Cu s 63.54 201.59 134.2

CuCO3 s 123.55 0 31.5
CuCl s 98.99 144.57 76.2
CuCl2 s 134.45 151.95 82.1
CuFe2O4 s 239.23 60.62 36.1
CuO s 79.54 44.27 6.5
Cu2O s 143.08 234.56 124.4

Standard
1 2 3 4 5
Cu(OH)2 s 97.55 –6.37 15.3
CuS s 95.00 873.87 690.3
Cu2S s 159.14 1049.1 791.8
CuSO4 s 159.60 155.65 89.8
Cu2SO4 s 223.14 377.15 253.6
D2 g 4.02946 249.199 263.8

D2O g 20.02886 0 31.2
D2O l 20.02886 –45.401 22.3
Fe s, D 55.847 412.12 374.3
Fe3C s, D cementite 179.552 1654.97 1553.9
FeCO3 s siderite 115.856 65.06 123.8
FeCl2 s 126.753 230.77 195.5
FeCl3 s 162.206 253.29 228.1
FeCr2O4 s 223.837 107.1 207.0
Fe0.947O s, wustite 68.8865 124.01 111.3
FeO s 71.846 140.16 124.9
Fe2O3 s, hematite 159.692 0 12.4
Fe3O4 s, magnetite 231.539 117.98 116.3
Fe(OH)3 s 106.869 –48.14 37.5
FeS s 87.911 1037.54 883.5
FeS2 s, pyrite 119.075 1684.72 1426.6
FeSO4 s 151.909 209.11 170.9
FeSi s 83.933 1249.42 1155.5
FeSiO3 s 131.931 118.07 159.9
Fe2SiO4 s, fyalite 203.778 255.3 232.3
FeTiO3 s 151.75 118.9 129.6
H2 g 2.01594 241.818 236.09

H g 1.00797 338.874 331.3
HCl g 36.461 108.82 84.5
HDO g 19.0213 0.21 18.8
HDO l 19.0213 –44.38 10.0
HNO3 l 63.0129 –53.19 43.5
H2O g 18.01534 0 9.5
H2O l 18.01534 –44.012 0.9
H3PO4 s 98.0013 –76.26 89.6
H2S g 34.08 946.61 812.0
H2SO4 l 98.077 153.25 163.4
APPENDIX 133

Standard
1 2 3 4 5
K s 39.102 356.63 366.6
KAlSi3O8 s, adulare 278.337 66.26 7.4
K2CO3 s 138.213 –43.58 85.1
KCl s 75.555 0 19.6
KClO4 s 138.553 6.67 136.0
K2Cr2O7 s 294.184 –190.4 34.3
KNO3 s 101.1069 –135.90 –19.4
K2O s 94.203 350.04 413.1
KOH s 56.109 52.72 107.6
K2S s 110.268 1024.4 943.0
K2SO3 s 158.266 300.47 302.6
K2SO4 s 174.266 4.62 35.0
K2SiO3 s 154.288 75.9 138.2
Mg s 24.312 725.71 626.1
MgAl2O4 s, spinel 142.273 274.17 45.3
MgCO3 s 84.321 23.43 30.2
MgCl2 s 95.218 244.65 158.2
MgFeO4 s 200.004 121.53 68,1
MgO s 40.311 124.38 59.1
Mg(OH)2 s 58.327 42.73 33.2
Mg(NO3)2 s 148.3218 –64.34 49.7
Mg3(PO4)2 s 262.879 76.59 78.1
MgS s 56.376 1105.11 893.9
MgSO4 s 120.374 166.22 73.0
MgSiO3 s 100.396 87.73 14.8
Mg2SiO4 s 140.708 188.35 59.8
Mg3Si2O5(OH)4 s, chrysilite 277.134 117.06 38.8
Mg3Si4O10(OH)2 s, talc 379.298 140.26 14.8
Mg2TiO4 s 160.52 231.48 119.2
Mn s, D 54.9381 520.03 487.7
Mn3C s 176.82545 1958.2 1878.5
MnCO3 s 114.9475 19.42 87.2
MnCl2 s 124.844 199.18 170.8
MnFe2O4 s 230.63 118.36 122.6
MnO s 70.9375 134.81 124.8
MnO2 s 86.0369 0 26.5
Mn2O3 s 157.8744 81.09 100.2
Mn3O4 s 228.8119 172.26 187.8

Standard
1 2 3 4 5
Mn(OH)2 s, amorphous 88.9528 66.47 112.7
MnS s, green 87.002 1031.23 878.9
MnSO4 s 151.000 180.2 147.8
MnSiO3 s 131.022 110.08 108.0
N2 g 28.0134 0 0.72
N2 atmospheric g 28.1541 0 0.69
NH3 g 17.0305 316.62 337.9
NH4Cl s 53.491 249.43 331.3
NH4NO3 s 80.04348 118.08 294.8
(NH4)2SO4 s 132.138 511.84 660.6
NO g 30.0061 90.25 88.9
NO2 g 46.0055 33.18 55.6
N2O g 44.0128 82.05 106.9
N2O4 g 92.011 9.163 106.5
N2O5 g 108.0104 11.3 125.7
Na s 22.9898 330.9 336.6

NaAlO2 s 81.9701 128.4 67.2
NaAlSi2O6·H2O s, analcime 220.055 35.41 20.3
NaAlSi3O8 s, low albite 262.2245 72.75 21.9
Na2CO3 s 105.9891 –75.62 41.5
NaCl s 58.443 0 14.3
NaHCO3 s 84.0071 –101.94 21.6
NaNO3 s 84.9947 –135.62 –22.7
Na2O s 61.979 243.82 296.2
NaOH s 39.9972 23.79 74.9
Na2S s 78.044 1014.84 921.4
Na2SO3 s 126.042 297.63 287.5
Na2SO4 s 142.041 0 21.4
Na2SiO3 s 122.064 11.31 66.4
Na2Si2O5 s 182.149 13.28 68.2
Na4SiO4 s 184.043 151.45 256.9
Ni s 58.71 239.74 232.7

Ni3C s 188.14 1180.09 1142.9
NiCO3 s 118.72 –49.93 36.4
NiCl2 s 129.62 94.85 97.2
NiO s 74.71 0 23.0
Ni(OH)2 s 92.72 –48.13 25.5
APPENDIX 135

Standard
1 2 3 4 5
NiS s 909.77 883.15 762.8
Ni3S2 s 240.26 1967.14 1720.2
NiSO4 s 154,77 92.25 90.4
NiSO4·6H2O s, D, tetragonal, 262.86 –266.75 53.6
green
O2 g 31.9988 0 3.97
O g 15.9994 249.17 233.7
O3 g 47.9982 142.67 168.1
P s, D, white 30.9738 840.06 861.4
P s, red, triclinic 30.9738 822.49 849.2
P4O10 s, hexagonal 283.8892 376.21 767.7
Pb s 207.2 305.64 232.8
PbCO3 s 257.2 0 23.5
PbCl2 s 278.1 106.67 42.3
PbO s, yellow 223.19 88.32 46.9
PbO s, red 223.19 86.65 45.9
PbO2 s 239.19 28.24 19.4
Pb3O4 s 685.57 198.53 72.2
Pb(OH)2 s 241.2 32.48 20.6
PbS s 239.25 930.64 743.7
PbSO4 s 303.25 111.12 37.2
PbSiO3 s 283.27 70.88 31.5
Pb2SiO4 s 506.46 159.07 75.8
S s, rhombic 32.064 725.42 609.6
SO2 g 64.0628 428.59 313.4
SO3 g 80.0622 329.7 249.1
Si s 28.086 910.94 854.9
SiC s, D, hexagonal 40.097 1241.69 1204.9
SiCl4 l 169.898 544.81 482.2
SiO2 s, D, quartz 60.085 0 2.2
SiO2 s, D, cristobalite 60.085 1.46 3.1
SiO2 s, amorphous 60.085 7.45 8.2
SiS2 s 92.214 2149.23 1866.6
Sn s, I, white 118.69 580.74 551.9

Sn s, II, gray 118.69 578.65 552.0

Standard
1 2 3 4 5
SnCl2 s 189.6 416.08 393.5
SnO s 134.69 294.97 297.0
SnO2 s 150.69 0 36.2
SnS s 150.75 1205.74 1063.2
SnS2 s 182.82 1863.8 1611.7
Ti s 47.90 944.75 907.2

TiC s 59.91 1154.16 1137
TiO s 63.9 425.14 419.2
TiO2 s, rutile 79.90 0 21.7
Ti2O3 s 143.80 368.66 386.1
Ti3O5 s 223.7 375.1 414.1
TiS2 s 112.03 2060.45 1876.2
U s 238.03 1230.1 1196.6

UCl3 s 344.39 577.35 556.0
UCl4 s 379.84 499.39 491.1
UCl5 s 415.3 536.93 519.5
UO2 s 270.03 145.19 168.9
UO3 s 286.03 0 49.8
U3O8 s 842.085 115.49 236.2
W s 183.85 842.87 827.5

WC s 195.86 1195.84 1199.5
WO2 s 215.85 253.18 297.5
WO3 s 231.85 0 69.3
WS2 s 249.98 2084.51 1796.6
Zn s 65.37 419.27 339.2

ZnCO3 s 125.38 0 23.9
ZnCl2 s 136.28 583.93 93.4
ZnFe2O4 s 241.06 74.08 32.2
ZnO s 81.37 70.99 22.9
Zn(OH)2 s, E 99.38 1918 25.7
ZnS s, sphalerite 97.43 938.71 747.6
ZnSO4 s 161.43 161.87 82.3
Zn2SiO4 s 222.82 112.74 18.1
APPENDIX 137
Table II: Group contribution for the enthalpy of devaluation and standard
chemical exergy of organic compounds*
Gases Liquids
Dq b qch Dq b qch
No Group kJ/mol kJ/mol kJ/mol kJ/mol
1 2 3 4 5 6
|
1 C 398.57 462.77 403.54 462.64
|
|
2 CH 509.77 557.40 485.75 545.27
|
|
3 CH 2 614.91 654.51 607.38 651.46
4 —CH3 713.47 747.97 715.35 752.03

|
5 = C 440.53 513.35 443.16 473.02
|
6 = CH 551.86 576.31 535.08 569.95
7 =CH2 660.26 678.74 680.26 675.68
8 =C= 543.04 554.23 539.28 559.21
9 { C 510.20 519.38 494.34 515.27
10 { CH 625.37 630.28 623.86 634.34

|
11 C (ring) 413.34 451.01 379.03 425.11
|
|
12 CH (ring) 522.78 561.37 468.76 543.05
|
|
13 CH 2 (ring) 629.05 662.29 614.16 653.63
|
14 = C (ring) 442.71 466.41 – –
chemical exergy of organic compounds (continued)
Gases Liquids
q q q q
D bch D bch
1 2 3 4 5 6
|
15 = CH (ring) 559.18 576.65 542.95 568.28
16 —O— 111.59 89.11 131.17 86.52
17 =O 246.86 245.09 91.46 –
18 —O— (ring) 117.42 97.12 126.27 106.64

§ | ·
19 —OH ¨ to C ¸ 68.42 165.48 137.54 80.08
¨© | ¸¹
§ | ·
20 —OH ¨ to CH¸ 63.90 66.78 85.11 52.59
¨© | ¸¹
§ | ·
21 —OH ¨ to CH 2 ¸ 56.66 42.89 84.82 51.34
¨© ¸¹
22 —OH (to CH3) 77.00 25.52 76.87 33.97
§ | ·
—OH ¨ to CH ring¸
23 ¨© | ¸¹ 65.16 46.78 70.47 58.16
—OH (attached to
24 66.12 52.01 81.64 47.57
aromatic)
|
25 C = O 262.38 293.87 231.58 281.36
|
26 H C= O 388.64 412.68 356.72 400.21
|
27 O =C O 65.69 108.30 35.90 101.15
APPENDIX 139
Gases Liquids
q q q q
D bch D bch
1 2 3 4 5 6
| |
O = C O C= O
28 296.94 382.66 244.81 362.70
|
29 O = C OH – 168.04 – 155.11
30 O CH = O 207.01 250.09 183.96 –

|
31 O = C (ring) – 305.66 – 277.76
|
|
H C= O
32 382.87 415.07 379.60 410.21
(attached to
aromatic)
|
33 N 97.03 142.05 64.60 131.09
|
34 NH 181.49 213.38 137.18 195.56
35 —NH2 258.43 290.20 235.43 284.39
36 =N— 56.82 72.98 103.43 –
37 {N 24.18 23.06 0 29.97

|
38 NH (ring) 186.19 209.24 151.20 199.37
—NH2
39 (attached to 237.80 240.16 216.84 269.24
aromatic)
|
NH (attached
40 153.58 196.27 – –
to aromatic)
Gases Liquids
q q q q
D bch D bch
1 2 3 4 5 6
|
N (attached
41 77.07 134.06 – –
to aromatic)
42 —NO2 42.30 1.45 58.32 12.16
43 —O—NO 19.66 18.89 – –
44 —O—NO2 89.91 89.77 121.71 23.88
45 —N=C— 585.26 592.73 551.97 584.03
46 N { C 516.93 527.50 510.53 522.14
47 —S— 761.07 636.88 741.74 642.32
48 —SH 862.06 724.36 848.67 732.26
49 =SO 692.04 553.78 696.47 566.88
|
50 SO 2 439.87 373.78 414.68 –
51 —S— (ring) 764.08 633.45 755.42 687.25

52 —F 15.00 16.25 8.85 34.70
53 —Cl 46.08 26.24 42.89 32.01
—F (attached to
54 15.08 45.16 8.85 34.70
aromatic)
—Cl (attached
55 46.08 26.24 42.89 32.01
to aromatic)
Ŷ56 Ortho (1,2) 4.35 7.66 0.0 0.0
Ŷ57 Meta (1,3) 1.76 3.47 0.0 0.0
Ŷ58 Para (1,4) 1.26 4.60 0.0 0.0
Ŷ59 1,2,3 position 12.89 20.08 0.0 0.0
Ŷ60 1,2,4 position 9.05 13.60 0.0 0.0
Ŷ61 1,3,5 position 6.28 14.27 0.0 0.0
Ŷ62 1,2,3,4 position 14.06 26.94 0.0 0.0
APPENDIX 141
Gases Liquids
q q q q
D bch D bch
1 2 3 4 5 6
Ŷ63 1,2,3,5 position 12.80 23.93 0.0 0.0
Ŷ64 1,2,4,5 position 12.38 24.27 0.0 0.0
1,2,3,4,5
Ŷ65 17.99 35.36 0.0 0.0
position
1,2,3,4,5,6
Ŷ66 19.66 62.34 0.0 0.0
position
3-atom
x67 62.30 49.04 83.68 83.68
saturated ring
4-atom
x68 50.84 43.76 87.82 82.30
saturated ring
5-atom
x69 50.38 45.52 0.0 0.0
saturated ring
6-atom
x70 83.05 61.25 28.79 0.0
saturated ring
7-atom
x71 73.81 46.32 – –
saturated ring
8-atom
x72 72.59 33.47 – –
saturated ring
x73 Pentene ring 50.38 45.52 0.0 0.0
x74 Hexene ring 83.05 61.25 28.79 0.0
*
Recalculated with permission from the data of Fan and Shieh [17] to the
reference level adopted in the present book.
Ŷ Branching in aromatic.
x Ring correction.
Table III: Standard chemical exergy of species dissolved in ideal aqueous

solutions (molarity 1 mol/kg H2O),Tn = 298.15 K, pn = 101.325 kPa
Standard chemical exergy
Undissociated Dissociated
Chemical q q
formula b kJ/mol
ch Form bch , kJ/mol
1 2 3 4
AgCl 59.4 Ag+, Cl– 77.9
CaCl2 – Ca2+, 2Cl– 19.7
CuCl – Cu+, Cl– 114.7
CuCl2 – Cu2+, 2Cl– 61.2
FeCl2 – Fe2+, 2Cl– 158.7
H2CO3 29.57 2H+, CO32– 124.6
H+, HCO3– 65.6
HCl 48.9 H+, Cl– 48.5
HF 56.6 H +, F – 74.6
HNO3 20.9 H+, NO3– 13.0
H3PO4 80.6 3H+, PO43– 204.4
2H+, HPO42– 134.1
H2S 817.9 – –
H2SO4 – 2H+, SO42– 108.6
KCl 15.0 K+, Cl– 14.6
KNO3 –19.8 K+, NO3– 20.7
KOH 46.9 K+ OH– 46.9
K2SO4 – 2K+, SP42– 41.3
LiCl 58.1 Li+, Cl– 29.7
MgCl2 – Mg2+, 2Cl– 40.4
NH3 327.4 – –
NH4OH 328.8 NH4+, OH– 322.1
Na2CO3 – 2Na+, CO32– 37.7
NaCl 5.5 Na+, Cl– 5.1
NaHCO3 21.4 Na+, HCO3– 21.4
NaNO3 29.4 +
Na , NO3– 30.2
NaOH 37.7 Na+, OH– 37.7
Na2SO4 – 2Na+, SO42– 22.2
O2 20.3 – –
PbCl2 – Pb2+, 2Cl– 69.5
ZnCl2 – Zn2+, 2Cl– 53.2
ZnSO4 51.8 Zn2+, SO42– 80.2
Solutions of exercises
1.1. The maximum energy efficiency of the prime mover, eqn (1.2) is KEmax = 0.667.
The exergy efficiency, eqn (1.8), KB = 0.582.
1.2. The exergy efficiency of the heat pump, eqn (1.9) KB = 1.025 > 1. The
information given in the prospectus is not credible.
1.3. The top and bottom temperature values in the considered Carnot cycle are Tmax
= 880 K, Tmin = 320 K. The energy efficiency of the considered prime mover is
0.636. The feeding heat flow rate Q f = 10/0.636 = 15.7 MW. The flow rate of heat
rejected to the environment Q 0 = 15.710 = 5.7 MW. The rates of exergy losses
result from eqn (1.17). For the feeding heat delivery
900 880
į B f = 15.7 u u 300 = 0.12 MW
900 880
Similarly for the rejection of the waste heat į B 0 = 0.36 MW.
1.4. The considered mixing process does not influence the enthalpy of CO2 or
atmospheric air nor the composition of air. Only the entropy of CO2 increases due to
its expansion. From eqn (1.22) it results:
R 100 000
įB = T0 ln = 111 kJ/kg
M 33
1.5. Heat delivered from the environment
q0 = ( 273 T1 ) u 2.14 + 333.4 + ( T0 273 ) u 4.18 = 438.4 kJ/kg
The entropy increase of the ice and liquid water:
273 333.4 293

's 2.14 u ln 4.14 u ln 1.597 kJ/(kg K)
263 273 273
The exergy loss:
§ q ·
įb T0 ¨ 's 0 ¸ 29.52 kJ
© T0 ¹
144 SOLUTIONS OF EXERCISES
2.1. The temperature-dependent component of exergy results from eqn (2.5a):
bphT = 26 882298 u 42.916 = 14 093 J/mol

From eqn (2.5b) it results that:
§ T · § 1100·
b phT ¦yicpi ¨ T T0 RT0 ln ¸ 33.525 u ¨ 1000 298 298uln ¸ 13840J/mol.
© T 0 ¹ © 298 ¹
i
The error of the approximate value amounts to 1.8%.

The pressure-dependent component of exergy results from eqn (2.6a)
bph p 8.3143 u 298 u ln 4.2 3556 J/mol
2.2. The specific chemical exergy of the considered combustion gases results from
eqn (2.26a):
bch 0.718 u 0.69 0.087 u 19.87 0.175 u 9.5 0.02 u 3.97

8.3143 u 103 u 298 u (0.718 u ln 0.718 0.087 u ln 0.087
0.175 u ln 0.175 0.02 u ln 0.02) 1.901 kJ/mol.
The ratio of the chemical exergy to the temperature-dependent component

of the physical exergy amounts to 0.135. In combustion processes the chemical
exergy of combustion gases represents one of the components of external exergy
losses. The possibilities of the utilization of this component are very small.
2.3. Specific enthalpy and entropy of the steam under consideration
h = 3483.3 kJ/kg, s = 6.592 kJ/(kg K)
At ambient temperature and pressure water appears in a liquid state
h0 = 83.9 kJ/kg, s0 = 0.296 kJ/(kg K)
The specific physical exergy amounts to
bph = 3483.3–83.9–293 (6.592–0.296) = 1554.7 kJ/kg.
The physical exergy may be determined also by means of the h,s diagram of steam
as a difference between the initial enthalpy and the enthalpy h2s after isentropic
expansion to the ambient isotherm:
bph = 3483.3–1931.3 = 1552 kJ/kg.
2.4. Different reference states for enthalpy and entropy are assumed in various
tables and diagrams. From the diagram in which the reference parameters hr = 0.5
MJ/kg, sr = 2.0 kJ/(kg K) for liquid ammonia at 0qC we obtain the specific enthalpy
and entropy of liquid ammonia at 15qC
h = 432.8 k/kg, s = 1.742 kJ/(kg K).
SOLUTIONS OF EXERCISES 145
For gaseous ammonia in standard state
h0 = 1859 k/kg, s0 = 7.608 kJ/(kg K).
The specific physical exergy:
bph = 432.8–1859–298u(1.742–7.608) = 321.9 kJ/kg.

2.5. Standard chemical exergy of SO2, table I
bch = 313.4 kJ/mol.
From eqn (2.10)

bch = –RT0 ln y0
313 400 = 8.3143u298uln y0, y0 = 1.16u10–55.
2.6. From the exergy balance of the standard reversible reaction of formation, eqn
(2.8)
bch = 2191.6 + 2u729.1 + 854.9 + 2u3.97 = 129.4 kJ/mol.
2.7. The compound B(OH)3 in aqueous solution has been accepted as a reference
species for B. The standard free energy of formation of the reference species
amounts to 968.8 kJ/mol. eqn (2.15) with the values j = 1, z = 0, b ch H2 = 236.1
kJ/mol, b ch O 2 = 3.97 kJ/mol, m = 3.4u10–4, J = 1 gives:
968.81.5u(236.1 + 3.97)8.3143u10–3u298uln (3.4u10–3) = 628.5 kJ/mol.
2.8. From the exergy balance of the considered standard reversible reaction, eqn
(2.7) it results that
'G q b ch CaSO 4 b ch SO 2 0.5 b ch O 2 b ch CaO

24.9 313.4 0.5 u 3.97 110.2 417.4 kJ/mol.
2.9. The free energy decrease (maximum work) of the considered reaction results
from the exergy balance. The chemical exergies of N2, O2 and CO2 contained in the
standard environment, equal zero:
q q
w max b ch CaCO 3 b ch Ca( NO 3) 2 16.3 1.4 19.1 kJ/mol 17.7 kJ/kg CaCO3.
The calculated value is much smaller than for technical fuels. The considered
reaction should run spontaneously in nature, but is kinetically blocked.
2.10. The ratio E according to the formula (2.18a):
4 8 1
ȕ 1.043 0.1896 u 0.0617 u 0.0428 u 1.0672
55 55 55
According to eqn (2.22):
bch = (24880 + 2442u0.1)u1.0672 + 9755u0.02 + 50u0.10 + 31.6u0.2

= 26 812 + 195 + 5 + 6 = 27 019 kJ/kg
The influence of water and ash content is very small. The ratio of the chemical
exergy to the lower heating value bch/CL = 1.086.
2.11. The contribution of chemical groups for the standard chemical exergy, taken
from table II is
CH=545.27 kJ/mol
F=34.70
Cl=32.01 u 2
bchq =643.99 kJ/mol
2.12. The number of moles of the particular elements per 1 kg of steel:
nFe 17.548, nC 0.5, nMn 0.1274, nS 0.0936, nP 0.0323, nSi 0.1068 mol
The number of moles of chemical compounds:
nMn3C 1/ 3 nMn 0.0425, nFe3C nC nMn 3C 0.4575 mol.
The amount of moles of free Fe:
cc
nFe nFe 3nFe3C 16.1755 mol.
Weighted sum of the chemical exergy values of the components:
¦nb i
i
q
ch i 7020 kJ/mol
Exergy decrease due to the formation of solution (assuming an ideal solution):
nT0 R ¦ y i ln y i 0.564 kJ/kg

i
The mixing component may be neglected.

2.13. The exergy efficiency of the boiler results from eqn (2.33). Assuming a
constant heat capacity of liquid water we obtain the mean thermodynamic
temperature of the heated water, eqn (2.34):
60
Tm 352 K
383
ln
323
From eqn (2.33):
0.86 § 263 ·
KB u ¨ 1 ¸ 0.199 .
1.09 © 352 ¹
2.14. The values determined in Exercise 2.3 may be used. The specific enthalpy and
entropy of feed water are: hw = 1038 kJ/kg, sw = 2.701 kJ/(kg K). The mean thermo-
dynamic temperature of the working fluid is
3483.3 1038
Tm 628.5 K
6.592 2.701
The exergy efficiency of the boiler amounts to 0.469.
2.15. Per 1 J of driving heat the amount of the produced useful heat is 1.6 J, and 0.6
J of bottom heat is absorbed from the partially utilized geothermal water. The mean
thermodynamic temperature values, eqn (2.34), and the values of the Carnot-factor,
eqn (1.5), are: heating water 391.6 K and 0.3156; bottom water 307.4 K and 0.1282;
useful water 331.6 K and 0.1918. The exergy efficiency of the heat pump:
1.6 u 0.1918
KB 0.782.
0.3156 0.6 u 0.1282
The calculated value is high, but it does not take into account the exergy losses
burdening the production of the driving heat.
3.1. The exergy efficiency of the considered heat pump, eqn (1.9), amounts to
0.255. The cumulative exergy efficiency is 0.0738.
3.2. Per 1 J of driving heat the cumulative consumption of fuel exergy (see table
3.1) is
*
b ch 1.06/ 0.88 1.205 J
The cumulative exergy efficiency of the considered heat pump is
* 1.6 u 0.1918
ȘB 0.239
1.205 0.6 u 0.1282
It is considerably smaller than the immediate exergy efficiency.

3.3. The cumulative exergy efficiency of the production of steel tubes, eqn (3.10), is
0.12.
3.4. Per 1 J of the chemical energy (or 1.09 J of exergy) of coal the amount of
produced electricity and useful heat is 0.208 and 0.692 J. The ratio of the exergy
increase to the enthalpy increase of network water amounts to 0.253. Hence, the
exergy increase of the network water is 0.175 J. The cumulative consumption of the
exergy of coal (per 1 J of chemical energy) is 1.121 J (see CExE of coal production,
table 3.1). The avoided cumulative consumption of coal exergy due to the
production of electricity is 0.208/0.29 = 0.717. Hence, the cumulative consumption
of coal exergy burdening the heat production is 1.1210.717 = 0.404. The

cumulative exergy efficiency of heat production is 0.175/0.404 = 0.433.
3.5. The CExC value for methanol:
* 3308 6082 425 283 554 u 1.06 45348 u1.04

b u 65 360 MJ/t.
0.29 0.40 425 0.785 0.98
The CExE value:
* 22410
ȘB 0.343
65360
3.6. The partial exergy losses burdening the production of particular energy carriers
and raw materials, per 1 t of methanol and in % of CExC are
§ 1 ·
electricity įb1 3308 u ¨ 1 8099 MJ/t 17.9%
© 0.29 ¸¹
425 283 § 1 ·
heat įb2 6082 u u¨ 1 1355 MJ/t 2.1%
425 © 0.4 ¸¹
§ 1 ·
coke įb 3 554 u 1.06 u ¨ 1 161 MJ/t 0.25%
© 0.785 ¸¹
§ 1 ·
natural gas įb 4 45348 u 1.04 u ¨ 1 962 MJ/t 1.5%.
© 0.98 ¸¹
įb5 1 0.343 0.179 0.021 0.002 0.015
production of methanol
0.44 44%
3.7. The CExC value:
* 2076 19 393 u 1.09 48 649 u 1.06 0.0077 u 7040

b
0.29 0.972 0.785 0.19
0.003 u 8200
= 95 035 MJ/t.
0.161
The CExE value:
* 281
ȘB 0.003 0.3%.
95 035
4.1. After introducing the intermediate heat carrier two heat exchangers will be
necessary to preheat the air. The heat flow rate in both heat exchangers will equal
that in a single heat exchanger, the heat transfer coefficient will be twice higher
and the mean temperature difference twice lower. Hence, the total necessary heat
transfer area will be twice larger.
4.2. In initial conditions the electric power delivered to the consumers amounts to:
B el E el 1000 u 0.45 u 0.82 u 0.9 332.1 MW
In the boiler the rate of the exergy increase of the working fluid is 450 MW. After
increasing the exergy loss in the boiler the rate of exergy increase of the working
fluid will be 440 MW, and the electric power delivered to the consumers will
decrease to:
Belc 440 u 0.82 u 0.9 324.7 MW .
If the additional exergy loss appears in the transformation and transmission system,
the electric power delivered to the consumers will be 322.1 MW. Hence, the in-
crease of the exergy loss is more disadvantageous in the final link of the system than
in the initial link.
5.1. The thermo-ecological cost should not take into account the consumption of
renewable exergy. Hence, the thermo-ecological cost per exergy unit of useful heat
(the sustainability index) is
ȡ 1.205
3.93
b 1.6 u 0.1918
The thermo-ecological cost per energy unit of useful heat is 0.753.

5.2. The specific enthalpy of the working fluid before its compression is h1 = 404.7
or 402.8 kJ/kg (first value for the heat extraction from the ground). The specific
enthalpy after compression is h2 = 441.8 or 445.8 kJ/kg. The specific enthalpy after
condensation h3 = 255.1 kJ/kg. The values of COP are 3.77 or 3.32. The ratio of the
exergy increase of the heated room to the amount of heat is 0.061. The cumulative
exergy efficiency of the heating system is 0.0718 or 0.0630. Hence, the index of
sustainability is 13.9 or 15.8. The utilization of the renewable source of bottom
heat slightly improves the sustainability index of the heating system, but its value
remains unfavorable.
5.3. The thermo-ecological cost of the energy unit of heat should take into account
its annual production and the annual cumulative consumption of exergy burdening
the production of metals and glycol:
ȡ 27 u 150.7 u 0.5 20 u 58.7.1 u 0.7 10 u 33.4 20 u 19.45/0.72

q 15 u 100 u 106 u 8760 u 3600
0.0789 J J th
The exergy increase of the heat carrier is
'b 281 313

1 u ln 0.0800.
q 15 298
The sustainability index is

ȡ
0.986.
'b
The obtained result is considerably smaller than in exercise 5.1, and fulfills the
condition of sustainability.
5.4. The thermo-ecological cost of the production of electricity should take into
account the mean annual consumption of steel, its recovery factor after wear and the
annual amount of the delivered electricity
ȡ 240 u 58 700 u 0.65
0.0943.
b 0.9 u 15 u 2000 u 3600
The calculated value expresses simultaneously the sustainability index. The
obtained result is very advantageous. Not all the used materials have been taken into
account. For example the additional consumption of copper would increase the
obtained result.
5.5. The energy efficiency of the power plant is related to the lower heating value.
Therefore, the ratio of the exergy to the lower heating value appears in the
calculation of the coal-fed plant and the ratio of the specific thermo-ecological cost
to the lower heating value is used when calculating the gas-fed plant. The thermo-
ecological cost of electricity when produced by means of coal is
1.09
ȡc 3.43
0.38 u 0.93 u 0.9
Electricity produced by means of gas has the thermo-ecological cost
683
ȡg 2.64
0.37 u 778 u 0.9
In the considered case the specific thermo-ecological cost equals the sustainability
factor. From the point of view of the economy of domestic non-renewable exergy
resources the application of imported gas is more advantageous, when compared
with coal.
6.1. The annual thermo-ecological cost of heating and thermal insulating per unit of
the wall area is
'Tm Ĳ R ȡ h įȡ p Ȗ A
PA + C
1 į Wl 1+ b į

k O
where: k = initial heat transfer coefficient of the wall
O, J, G, = thermal conductivity, mass density and thickness of the thermal
insulation
'Tm = mean temperature difference between the heated room and the
environment in the heating season
WR = annual duration of the heating season

Uh, Up = specific thermo-ecological cost of useful heat and thermal insulation
Wl = life time of the thermal insulation layer,
k Ȗȡp
A 'Tm kĲ R ȡ h , b , C
Ȝ Ĳl
The optimum insulation thickness is
1 § Ab ·
į opt 1¸
b ¨© C ¹
Introducing the given data we obtain:
A = 600.5 MJ/(m2 a), b = 32.5 1/m, C = 165 MJ/(m3 a), Gopt = 0.304 m.
7.1. According to eqn (7.7) and Example 7.3 the discounted rate of the pro-
ecological tax is 0.0044u1.752 = 0.0077 US$/MJ. The pro-ecological tax which
should be added to the selling price of electricity is
12 000 u 0.0077
0.0034 US$/kWh
0.9 u 15 u 2000
The determined value is considerably smaller than in Example 7.2.

7.2. The energy efficiency of the boiler represents the amount of useful heat per unit
of the heating value of coal. Hence, the pro-ecological tax which should be added to
the selling price of a heat unit is
1.12
u 4.4 5.8 US$ GJ
0.85
7.3. The value of COP represents the amount of useful heat per unit of driving
electricity. Hence, the pro-ecological tax which should be added to the selling price
of a heat unit to reimburse the tax paid for the purchase of electricity is
3.13
u 4.4 3.9 US$ GJ .
3.5
The total amount of heat produced during the life time per 1 kW of thermal power is
3500u20u3600u10–6 = 252 GJ
The corrected rate of the tax resulting from eqns (7.6) and (7.7):
0.0044 u 20 u 0.08
0.00898 US$ MJ 8.98 US$ GJ
1 1.0820
The tax component which should reimburse the initially paid tax burdening the
purchase of installation:
15 u 8.98
0.53 US$ GJ
252
The total tax is 3.9+0.53 = 4.43 US$/GJ.

7.4. The reduction of the annual thermo-ecological cost of heat per 1 m2 of the wall:
§ ·
¨ 1 ¸ § 1 ·
P Pc 'T ¨ k Ĳ ȡ 18 u ¨1.3 ¸ u 5.4 u 3.6 u 1.32
m 1 į¸ R h © 5.79 ¹
¨ ¸
© k Ȝ¹

520.9 MJ m 2 a
The thermo-ecological cost of thermal insulation:
Up = 0.2u20u165 = 660 MJ/m2

The total discounted value of the reduction of the pro-ecological tax (net present
value NPV) is
§ 1 · ª 1§ 1 ·º
0.0044 u ¨ ȡ p ȡ h ¦ t ¸
0.0044 « ȡ p ȡ h ¨1 ¸»
© t 1 r ¹ «¬ r © 1 r Ĳ ¹ »
¼
19.6 $ m 2
References
[1] Ahrendts, J., The exergy of chemically reacting systems (in German),
VDI Forschugsheft 579, VDI, Düsseldorf, 1977.
[2] Ayres, R.U., Ayres, L.W. & Martinas, K., Eco-thermodynamics: exergy
and life cycle analysis. CMER, INSEAD, Fontainebleau, 1996.
[3] Baehr, H.D., Definition and calculation of exergy and anergy (in
German). Brennstoff-Wärme-Kraft, 17(1), pp. 1–6, (1965).
[4] Bejan, A., Entropy generation minimization: the new thermodynamic of
finite-size devices and finite-time processes. Journal of Applied Physics
Reviews, 79, (1996), February.
[5] Berg, M.D. van Kool, H.J. & van Swaan Arons, J. de, A thermodynamic
basis for sustainability. Proceedings of ECOSS’99, In: eds. M. Ishida et
al. Tokyo, pp. 270–281, 1999.
[6] Bibrowski, Z. (ed.), Cumulative consumption of energy (in Polish).
PWN, Warszawa, 1983.
[7] Bošnjakoviü, F., Fight against Irreversibilities (in German). Archiv für
Wärmewirtschaft, 19(1), pp. 1–2, (1938).
[8] Boustead, I. & Hancock, G.F., Handbook of industrial energy analysis.
Ellis Horwood, Chichester, 1979.
[9] Brodyanskyi, W.M., Exergy method in thermodynamic analysis (in
Russian), Energyia, Moskov, 1973.
[10] Brodyanskyi, W.M., Sorin, M.V. & le Goff, P., The efficiency of
industrial processes: exergy analysis and optimization. Elsevier,
London, 1994.
[11] Bullard, III C.W. & Herendeen, R.A., The energy costs of goods and
services. Energy Policy, 3(4), pp. 268–278, 1975.
[12] Chapman, P.F., 1. Energy costs: a review of methods. Energy Policy,
2(2), pp. 91–103, 1974.
[13] Chapman, P.F., Learch, G. & Slesser, H., 2. Energy costs of fuels. Energy
Policy, 2, pp. 231–243, 1974.
[14] Chiesa, P., Lozza, G., Macchi, E. & Consoni, S., An assessment of the
thermodynamic performance of mixed gas-steam cycles: part B — water
injected and HAT cycles. Trans. ASME, Journal of Engineering for Gas
Turbine and Power, 17, pp. 409–508, 1995.
154 REFERENCES
[15] Conelly, L. & Koshland, C.P., Exergy and industrial ecology — part 1: an
exergy-based definition of consumption and thermodynamic inter-
pretation of ecosystem evolution. Exergy, an International Journal, 1(3),
pp. 146–164, 2001.
[16] Conelly, L. & Koshland, C.P., Exergy and industrial ecology — part 2: a
non-dimensional analysis of means to reduce resource depletion. Exergy,
an International Journal, 2(1), pp. 1–23, 2002.
[17] Fan, L.T. & Shieh, J.H., Group contribution for specific chemical
enthalpy Eq, specific chemical entropy jq and specific chemical exergy Hq,
1985 (Tables obtained from the authors).
[18] Frangopoulos, C.A., An introduction to environment analysis and
optimization of energy intensive systems. Proceedings of ECOS’92. In:
eds. A. Valero & G. Tsat-saronis, Zaragoza, pp. 231–239, 1992.
[19] Fratzscher, W., Brodyanskyi, V. & Michalek, K., Exergy; theory and
application (in German). VEB, Leipzig, 1986.
[20] Gaj, H., Calculation method of ecological economic losses (in Polish).
Gospodarka Paliwami i Energia, 9, pp. 10–13, 1991.
[21] Gates, D.M., The flow of energy in the biosphere. Scientific American,
225(3), pp. 89–100, 1971.
[22] Gibbs, J.W., On the equilibrium of heterogeneous substances, The
Scientific Papers, In: ed. J.W. Gibbs, v. 1, Dover Publ., New York, 1961.
[23] Gong, M. & Wall, G., On exergetics, economics and optimization of
technical processes to meet environmental conditions. Proceedings of
TAIES’97, In: eds. R. Cai, M.J. Moran, S. Zhang, & Y. Xiao, Beijing,
World Publishing Corporation, pp. 453–460, 1997.
[23] Gouy, G., About available energy (in French). Journal de physique II, 8,
pp. 501–518, 1889.
[24] Grassmann, P., The exergy and the flow diagram of the technically
available power (in German). Allgemeine Wärmetechn. 9(4/5), pp. 79–86,
1959.
[25] Guidelines for energy analysis. International Federation of Institutes for
Advanced Study Stockholm, 1974.
[26] Heinsohn, R.J. & Kabel R.L., Sources and control of air pollution,
Prentice Hall: New Jersey, 1999.
[27] Hubbert, M.K., The energy resources of the Earth. Scientific American,
225(3), pp. 60–70, 1971.
[28] Iantovski, E., What is exergonomics? (on a branch of engineering
thermodynamics). In: Proceedings of FLOWERS’97. Florence, pp. 1163–
1176, 1997.
[29] Iantowski, E., Exergonomic optimization of temperature drop in heat
transfer through a wall. Proceedings of ECOS’98. In: eds. A. Bejan et al.,
Nancy, pp. 339–346, 1998.
[30] Keenan, J.H., Availability and irreversibility in thermodynamics. British
Journal of Applied Physics, 2, pp. 183–192, 1951.
REFERENCES 155
[31] Kotas, T.J., The exergy method of thermal plant analysis. Butterworths,
London, 1985.
[32] Learch, G., Energy and food production. Guildford, London, 1976.
[33] Leites, I.L. Sama, D.A. & Lior, N., The theory and practice of energy
saving in the chemical industry: some methods for reducing thermo-
dynamic irreversibility in chemical technology processes. Energy, the
International Journal, 28(1), pp. 55–97, 2003.
[34] Linnhoff, B., Pinch technology for the synthesis of optimal heat and
power systems. Trans. of ASME, Journal of Energy Resources
Technology, 111(3), pp. 137–147, 1989.
[35] Lior, N., Irreversibility of combustion. Proceedings of ECOS’01, In: eds.
A. Öztürk & Y. Gögüs, Istanbul, pp. 39–48, 2001.
[36] Mejro, Cz., Principles of energy management, (in Polish). WNT, Warsaw,
1980.
[37] Morris, D.R. & Steward, F.R., Exergy analysis of a chemical
metallurgical process. Met. Trans., 15B, pp. 645–654, 1984.
[38] Morris, D.R. & Szargut, J., Standard chemical exergy of some elements and
their compounds on the planet Earth. Energy, 11(8), pp. 733–755, 1986.
[39] Nerescu, I. & Radcenko, V., Exergy analysis of thermal processes (in
Rumanian), Editura Tehnica, Bucuresti, 1970.
[40] Petela, R., Exergy of heat radiation. Journal of Heat and Mass Transfer
Ser. C, 86, pp. 187–192, 1964.
[41] PolaĔski, A. & Smulikowski, K., Geochemistry (in Polish), Wydawnictwa
Geologiczne, Warsaw, 1969.
[42] Rant, Z., Exergy, a new word for “technical available work” (in German).
Forsch. Ing.-Wes. 22(1), pp. 36–37, 1956.
[43] Rant, Z., Exergy and anergy (in German). Wissenschaftliche Zeitschrift
Techn. Univ. Dresden, 13(4), pp. 1145–1149, 1964.
[44] Ranz-Villarino, L., Valero, V. & Cebollero, M., Application of
Szargut’s methodology to an exergetic account of Earth’s mineral
capital. Proceedings “Contemporary Problems of Thermal
Engineering” In: eds. Z. Rudnicki, J. Skorek & A. ZiĊbik, Gliwice-
UstroĔ, pp. 263–274, 1998.
[45] Rasheva, D.A. & Atanasova, L.G., Exergy efficiency evaluation of the
production of sulfur acid from liquid sulfur. Exergy, the International
Journal, 2(1), pp. 51–54, 2002.
[46] Repetto, R., Dover, R., Jenkins, R. & Georghegan, J., Green fees, how a
tax shift can work for the environment and the economy. World Resource
Institute, Washington, 1992.
[47] Riekert, L., The efficiency of energy utilization in chemical processes.
Chem. Eng. Sci., 29(29), pp. 1613–1620, 1974.
[48] Sama, D., A common sense 2nd law approach to heat exchanger network
design. Proc. ECOS’92, In: eds. A. Valero & G. Tsatsaronis, Zaragoza,
pp. 329–338, 1992.
156 REFERENCES
[49] Sciubba, E., A novel exergetic costing method for determining the
optimal allocation of scarce resources. Proceedings of the conference
“Contemporary Problems of Thermal Engineering”, Technical
University of Silesia, In: eds. Z. Rudnicki et al., Institute of Thermal
Technology: Gliwice-UstroĔ, pp. 311–324, 1998.
[50] Sciubba, E., Cost analysis of energy conversion systems via a novel
resource-based quantifier. Energy, 28(5), pp. 457–477, (2003).
[51] Slesser, M., Unitax: a new environmentally sensitive concept in taxation.
Hydatum Press: Ross-on-Wyse, 1989.
[52] Smil, V., Energies, 2nd ed. The MIT Press, Massachusetts, 1999.
[53] Stanek, W., System analysis of the choice of thermal parameters of blast
and of the addition of auxiliary fuels in a blast-furnace process (in
Polish). PhD thesis, Institute of Thermal Technology, Technical
University of Silesia, Gliwice, 1999.
[54] Stanek, W., Iterative method to evaluate the ecological cost of imported
goods. International Journal of Applied Thermodynamics, 4(4), 191–198,
2001.
[55] Stodola, A., The cyclic processes of the gas engine (in German).
Zeitschrift der VDI, 23(38), pp. 1086–1091, 1898.
[56] Szargut, J., Potential balance of physical processes, resulting from the 2nd
law of thermodynamics (in Polish). Arch. Budowy Maszyn, 3(3), pp. 231–
276, 1956.
[57] Szargut, J., Potential balance of chemical processes (in Polish). Arch.
Budowy Maszyn, 4(11), pp. 89–117, 1957.
[58] Szargut, J. & Styrylska, T., Approximate evaluation of the exergy of fuels
(in German), Brennstoff-Wärme-Kraft, 16(12), pp. 589–596, 1964.
[59] Szargut, J., Exergy balance of metallurgical processes (in Polish).
Archiwum Hutnictwa, 6(1), pp. 23–60, 1961.
[60] Szargut, J. & Petela, R., Exergy (in Polish). PWN, Warszawa, 1965.
[61] Szargut, J., The limits for the application possibilities of exergy concept
(in German). Brennstoff-Wärme-Kraft, 19(6), pp. 309–313, 1967.
[62] Szargut, J., Minimization of the consumption of natural resources.
Bulletin of the Polish Academy of Sciences, Technical Sciences, 26(6),
pp. 42–45, 1978.
[63] Szargut, J. & Maczek, K., Thermoeconomic estimation of the optimum
exergetic efficiency of refrigeration system. Proc. of Intern. Congress of
Refrigeration, Paris 1983, Comm. B2, pp. 119–124.
[64] Szargut, J. & Morris, D.R., Calculation of the standard chemical exergy
of some elements and their compounds based upon sea water as the datum
level substance. Bulletin of the Polish Academy of Sciences, Technical
Sciences, 33(5-6), pp. 293–305, 1985.
[65] Szargut, J., Application of exergy for the calculation of ecological cost.
Bulletin of the Polish Academy of Sciences, Technical Sciences, 34(7-8),
pp. 475–480, 1986.
REFERENCES 157
[66] Szargut, J., Standard chemical exergy of some elements and their com-
pounds, based upon the concentration in Earth’s crust. Bulletin of the Polish
Academy of Sciences, Technical Sciences, 35(1-2), pp. 53–60, 1987.
[67] Szargut, J. & Morris, D.R., Cumulative exergy consumption and cumulative
degree of perfection of chemical processes. Energy Research, 11(11), pp.
245–261, 1987.
[68] Szargut, J., Influence of the imported goods on the cumulative energy
indices. Bulletin of the Polish Academy of Sciences, Technical Sciences,
35(9-10), pp. 591–595, 1987.
[69] Szargut, J., Morris, D.R. & Steward, F.R., Exergy analysis of thermal,
chemical and metallurgical processes. Hemisphere Publ. Corp.: New York,
1988.
[70] Szargut, J., Reference level of chemical exergy. Archiwum Termodynamiki,
9(1-2), pp. 41–52, 1988.
[71] Szargut, J., Chemical exergies of the elements. Applied Energy, 32, pp. 269–
285, 1989.
[72] Szargut, J., Analysis of the cumulative exergy losses at the production and
delivery of heat from the HP-plant (in Polish). Archiwum Energetyki, 4, pp.
187–203, 1989.
[73] Szargut, J. & Majza, E., Thermodynamic imperfection and exergy losses at
the production of pig iron and steel. Archiwum Hutnictwa, 2, pp. 197–216,
1989.
[74] Szargut, J., Gross and net exergy losses in the technological networks.
Bulletin of the Polish Academy of Sciences, Technical Sciences, 40(5), pp.
69–77, 1992.
[75] Szargut, J. & Sama, D.A., Practical rules of the reduction of energy losses
caused by the thermodynamic imperfection of thermal processes. Proc. The
Second Intern. Thermal Energy Congress, In: eds. E. Bilgren et al., Agadir,
pp. 782–785, 1995.
[76] Szargut, J., Exergy and ecology. In: eds. E. Sciubba & M.J, Moran, Proc. of
the Workshop Second Law Analysis of Energy Systems, Roma, pp. 11–19,
1995.
[77] Szargut, J., Depletion of the unrestorable natural exergy resources, Bulletin
of the Polish Academy of Sciences, Technical Sciences, 45(2), pp. 241–250,
1997.
[78] Szargut, J., Problems of thermodynamic optimization. Archives of
Thermodynamics, 19(3-4), pp. 85–94, 1998.
[79] Szargut, J. & Skorek, K. Results of experimental investigations of the non-
throttling Granryd refrigerator. International. Journal. of Energy Research,
23, pp. 1325–1330, 1999.
[80] Szargut, J., Depletion of the unrestorable natural exergy resources as a
measure of the ecological cost, Proceedings of ECOS’99, Tokyo Institute of
Technology, In: eds. M. Ishida, G. Tsatsaronis, M.J. Moran, & H. Kataoka,
pp. 42–45, 1999.
158 REFERENCES
[81] Szargut, J. & ZiĊbik, A., Principles of thermal energetics (in Polish), 2nd
ed. PWN, Warszawa, 2000.
[82] Szargut, J., Sequence method of determination of partial exergy losses in
thermal systems, Exergy, an Intern. Journal, 1(2), pp. 85–90, 2001.
[83] Szargut, J., Low-exergy heating systems—when can they be profitable.
In: ed., St. MierzwiĔski, Proceedings of 50. Executive Committee
Meeting, International Energy Agency, Energy Conservation in Buildings
and Community Systems Programme, Krakow, November 7, pp. 75–80,
2001.
[84] Szargut, J., Comparison of the variants of primary gas turbine supple-
menting a coal-fired power plant. ECOS’01. July 4–6, 2001 Istanbul, pp.
325–330.
[85] Szargut, J., Application of exergy for the determination of the pro-
ecological tax replacing the actual personal taxes. Energy, (27), 379–389,
2002. Letter to the editor. Energy, 28, pp. 591–592, 2003.
[86] Szargut, J., ZiĊbik A. & Stanek W., Depletion of the non-renewable
natural exergy resources as a measure of the ecological cost. Energy
Conversion & Management, 42, pp. 1149–1163, 2002.
[87] Szargut, J., Technical thermodynamics, III Ed. (in Polish), Wydawnictwo
Politechniki ĝląskiej, Gliwice, 2000.
[88] Szargut, J., Anthropogenic and natural exergy losses (exergy balance of
the Earth’s surface and atmosphere). Energy, the Intern. Journal, 28(11),
pp. 1047–1054, 2003.
[89] Szargut, J., Skorek J. & Szczygieá I., Influence of blade cooling on the
efficiency of the humid air turbine. International Journal of Applied
Thermodynamics, 3(1), pp. 21–26, 2000.
[90] Szczygieá, I., Influence of the after cooler on the efficiency of the humid
air turbine. International Journal of Applied Thermodynamics, 4(4), pp.
165–171, 2001.
[91] Taylor, S.R. & McLennan, S.M., The continental crust: its composition
and evolution. Blackwell Scientific Publications: London, 1985.
[92] Taylor, S.R. & McLennan, S.M., The geochemical evolution of the
continental crust. Revue of Geophysics, 33, pp. 241–265, 1995.
[93] Todd, D., Clean coal technologies for gas turbines. GE Power Gene-
ration, GER-36-508, 1992.
[94] Tribus, M. & Evans, R., Thermoeconomics. UCLA Report No 52-63, 1962.
[95] Tsatsaronis, G. & Cziesla, F., Thermoeconomics. Proc. of the Sym-
posium of the Centre of Excellence OPTI—ENERGY, Silesian University
of Technology, Institute of Thermal Technology, Gliwice, pp. 77–92,
June 2003.
[96] Tsatsaronis, G., Some thoughts regarding the worldwide effective use of
energy resources and the reduction of environmental impact. Advances in
Energy Studies, Exploring Supplies, Constraints and Strategies, In: eds.
Ulgiati et al., SGE Publisher: Padova, 2001.
REFERENCES 159
[97] Valero, A., Torres, C. & Serra, L., A general theory of thermo-economics,
part I, structural analysis. Proc. ECOS’92, In: eds. A. Valero & G.
Tsatsaronis, Zaragoza, pp. 137–145, 1992.
[98] Valero, A. & Lozano, M.A., A general theory of thermoeconomics, part
II, the relative free energy function. Proc. ECOS’92, In: eds. A. Valero &
G. Tsatsaronis, Zaragoza, pp. 147–154, 1992.
[99] Valero, A., Ranz, L. & Botero, E., An exergetic assessment of natural
mineral capital (1), reference environment, a thermodynamic model for
degraded Earth. Proc. ECOS’02, In: eds. G. Tsatsaronis, M.J. Moran, F.
Cziesla & T. Bruckner, Berlin, pp. 54–61, 2002.
[100] Valero, A. & Botero, E., Exergetic evaluation of natural mineral capital
(2), application of methodology to current world reserves. Proc.
ECOS’02, In: eds. G. Tsatsaronis, M.J. Moran, F. Cziesla & T. Bruckner,
Berlin, pp. 62–68, 2002.
[101] Valero, A., Botero, E. & Serra, L., The exergy replacement cost of the
world’s renewable water resources and ice sheet. Proc. ECOS’02, In: eds.
G. Tsatsaronis, M.J. Moran, F. Cziesla & T. Bruckner, Berlin, pp. 158–
164, 2002.
[102] von Weizsäcker, E.U., Lovins, A.B. & Lovins, L.H., Factor four. Doubled
well-being—twice smaller consumption of natural resources (in German).
1996, Droemersche Verlaganstalt, München, 1996.
[103] Wall, G., Exergy—a useful concept within resources accounting. Report:
Physical Resources Theory, Chalmers, S-412 96, Göteborg, 1977.
[104] Wall, G., Bibliography on exergy, Chalmers University of Technology
and University of Göteborg, 1987.
[105] Wall, G., Exergy, ecology and democracy—concepts of vital society.
Proceedings of ENSEC'93, In: eds. J. Szargut, Z. Kolenda, G. Tsatsaronis,
& A. Ziebik, Cracow, pp. 111–121, 1993.
[106] Wall, G. & Gong, M., On exergy and sustainable development—Part 1,
Conditions and concepts. Exergy, an International Journal, 1, pp. 128–
145, 2001.
[107] Wilk, R., Principles of low-emission combustion (in Polish). Polish
Academy of Sciences, Division Katowice, Katowice: Wydawnictwo
Gnome, 2000.
[108] Witczak, M., Kinetics and modelling of the synthesis of lower acrylate
and methacrylate (in Polish), PhD Thesis, Institute of Chemical
Engineering of the Polish Academy of Sciences, Gliwice, 2000.
[109] Rivero, R. & Garfias, M., Standard chemical exergy updated. Part II. In:
Proceedings of ECOS 2004, Guanajuato, Mexico.
Index
Absorption of thermal radiation, 14 machine, 7
Activity coefficient, 27 Chemical exergy, 21, 39
Adiabatic: Coal, chemical exergy of, 35
combustion, 13 Coefficient:
compression, 88 of by-production, 60
expansion, 86 of consumption, 60, 64
Aftercooler, 89 of performance (COP), 52
Ahrendts J., 22 of sensibility, 8
Air, atmospheric reference species, 24 Cogeneration, 68, 89
Anergy, 9 Coke:
Anthropogenic exergy losses, 16 chemical exergy of, 35
Atanasova, 52 production, 67
Availability, ix Combined (complex) processes, 8
Avoided expenditures, 60, 107 Combustion, 13, 88
Back-pressure turbine, 72 Compression:
heat pump, 5, 48, 72, 103
Baehr H.D., 9
refrigerator, 48
Balance:
Compressor, 42, 87
of cumulative exergy
Condenser, 10, 86
consumption, 59
Cost of:
of thermo-ecological cost, 91
exergy, 90, 105
of energy, 5, 43, 46
exergy losses, 105
of exergy, 4, 42, 46, 49, 51
Counter-current process, 78
Black body emission, 14
Cumulative:
Blast furnace, 63, 99
exergy consumption, 57, 64
Boiler:
exergy efficiency, 60, 73
efficiency, 44
exergy loss, 63
exergy losses, 46
Boundary of system, 4 Depletion of non-renewable
Bošnjakovi F., ix resources, 91
Brodyanskyi W.M., ix Devaluation:
By-product, 63, 98, 108 enthalpy of, 34
Calcium carbide production, 69 reaction of, 37
Carnot M.L.S., 1 Diffusion, 12
162 Index
Discounted coefficient, 126 definition, 1

Dissipative structure, 16 economic application of, 105
Dissociation, 13 efficiency, 6, 52, 61
Domestic consumption product, 92, 95 losses, 3, 76, 89
cumulative, 63
Ecological cost, see: external, 3, 42
thermo-ecological cost internal, 3, 43
Economic optimization, 115 natural, 16
Efficiency: partial, 63, 72
electro-mechanical, 46 nuclear, 41
exergy, 6, 60 of radiation, 38
of fuel delivery, 61 physical, 19
of transformation and types, 19
transmission, 61 Export of domestic products, 127
Emission, 14
Energy: Free Gibbs energy, 24
balance, 5 Fresh water, 118
efficiency, 7, 42, 44, 97, 104 Friction: 20
Enthalpy: heat, 20
chemical (chemical energy), 34 Fuel exergy, 35
of devaluation, 34
physical, 20 Gaggioli, 75
Entropy: Gas turbine, 42, 47, 53, 77, 79,
flux of radiation, 14 Gibbs J.W., ix
generation, 3, 15, 107 Gibbs free energy, 24
Environment: Gouy-Stodola law, 3
standard concentration of Gouy G., ix
reference species, 25 Grassmann P., 4
temperature, 2 Green-house effect, 17
Esterification, 76 Group contribution method, 36, 137
Evaluation of natural resources, 91 Heat:
Evaporation plant, 86 exchanger, 76, 109, 112
Evaporator, 86 pump, 5, 48, 52, 128
Exergetic cost, 114 source, 1, 4
Exergonomics, 105 transfer, irreversibility of, 10
Exergy: Heat-and-power plant, 8, 64, 71, 86
balance, 4, 42, 46, 49, 51 Heating value, 35
calculation, 19 Heat-and-power plant, 8
chemical, 21 Human work, 58
of fresh water, 119 Humid air turbine, 88
of fuels, 35 Humidity of air, 25
of nitrates, 27
of solutions, 37 Imported goods, 101, 127
components, 19 thermo-ecological cost of, 101
cumulative consumption of, 57 Improvement of processes, 75
Index 163
Input-output equations, 59, 94, 124 Partial exergy losses, 63, 65, 72
Intermediate heat carrier, 83 Personal tax, 122
Investment: Petela R., ix, 39
cost, 113, 115 Pig iron, 66, 98
efficiency, 61 Power plant, 1, 16, 41, 47, 61, 78
Ionic reference species, 26 Preheating of combustion reactants,
strength, 28 14
Irreversibility: Pressure loss, 109, 112
of adiabatic expansion, 9 Prime mover, 5, 38
of combustion, 13 Principle of avoided expenditures,
of radiation emission and 60, 63, 107
absorption, 16 Product:
of heat transfer, 10 major, 60
of mixing, 12 semi-finished, 57
Pro-ecological tax, 121
Keenan J.H., ix
Kinetic exergy, 19 Radiation:
exergy of, 38
Leites, 90 relict, 41
Limestone, 45 solar, 39
Linde cycle, 84 Rant Z., ix, 2, 9
Lior N., 25, 90 Reaction of formation, 24
Maximum work, 2 Recirculation, 77
Mixing, 77 Reference:
Morris D.R., ix, 27 level, 22
reaction, 22
Natural: species, 22
exergy losses, 16 dissolved in seawater, 27
losses of utilizable exergy, 39 ionic, 25, 28
gas, 95, 100, 101 gaseous, 24
mineral capital, 118 solid, 26
non-renewable resources, 91, 94 standard concentration of,
Net coefficient of consumption, 64 25
Net present value, NPV, 152 Refrigerator, 48
Nitrates, chemical exergy, 27 Repetto R., 121
Number of thermoeconomic Replacement ratio, 60, 63, 109
similarity, 116 Reynolds number (Re), 110
Riekert L., 2
Operational cost, 110, 113
Optimization: Sama D., 3, 75, 90
economic, 116 Sciubba E., iii, 115
objective function, 108 Seawater:
of thermo-ecological cost, 108 molarity of elements, 38
of exergetic cost, 114 reference species, 26
Oxygen, 12, 22, 28, 62, 76, 98 salinity, 25
164 Index
Second law of thermodynamics, ix, 2 Temperature:

Sequence analysis, 68 exergy scale, 11
Slesser M., 121 mean thermodynamic, 45
Solar: Thermo-ecological cost 92, 108
collector, 104 of exported goods, 94, 102
radiation, 39 of imported fuels, 101
Solution, chemical exergy of, 36, 142 of waste products, 95
Standard chemical exergy: Thermodynamic imperfection, ix, 57
data, 39 Thermoeconomics, 105
definition, 23 Throttling, 12, 84
group contribution, 35 Tsatsaronis G., 105, 122
Stanek W., iii, 100, 102, 122, 123, Unitax, 121
127
Valero A., 116, 118
Steam:
Value added tax, VAT, 121
boiler, 44
power plant, 48, 87 Wall G., 41, 121
turbine, 45, 66, 72, 85 Waste heat boiler, 85
Stefan-Boltzmann constant, 14 Waste products, 3, 53, 91, 95, 99
Stodola A., ix aggressive components, 96
Styrylska T., 35 index of harmfulness, 91
Substitution ratio = replacement Water:
ratio boiler, 128
Sulfuric acid plant, 52 preheater, 111
Sustainability index, 102 resources, 118
System boundary, 5, 19 Weizsäcker von, 122
Wind power plant, 104, 128
New Journals from Modelling and Simulation
WIT Press of Turbulent Heat
Transfer
In 2005 WIT Press will be launching the Editors: B. SUNDÉN, Lund Institute of
International Journal of Ecodynamics, Technology, Sweden and M. FAGHRI,
the International Journal of University of Rhode Island, USA
Sustainable Development & Planning
and Design & Nature: A Providing invaluable information for both
graduate researchers and R & D engineers
Transdisciplinary Journal Relating
in industry and consultancy, this book
Nature, Science and the Humanities. focuses on the modeling and simulation of
Designed to facilitate interdisciplinary fluid flow and thermal transport phenomena
communication, these will be available in turbulent convective flows. Its overall
both online and in paper format. For further objective is to present state-of-the-art
information please contact: knowledge in order to predict turbulent heat
harnold@witpress.com. transfer processes in fundamental and
idealized flows as well as in engineering
applications.
The chapters, which are invited
contributions from some of the most
prominent scientists in this field, cover a
wide range of topics and follow a unified
outline and presentation to aid accessibility.
Series: Developments in Heat Transfer,

Vol 16
ISBN: 1-85312-956-9 2005 360pp

WIT eLibrary £124.00/US$198.00/€186.00
Home of the Transactions of the Wessex

Institute, the WIT electronic-library
provides the international scientific
community with immediate and permanent
access to individual papers presented at
WIT conferences. Visitors to the WIT
eLibrary can freely browse and search
abstracts of all papers in the collection WITPress
before progressing to download their full Ashurst Lodge, Ashurst, Southampton,
text. SO40 7AA, UK.
Tel: 44 (0) 238 029 3223
Visit the WIT eLibrary at Fax: 44 (0) 238 029 2853
http://www.witpress.com E-Mail: witpress@witpress.com
Condensation Heat Heat and Fluid Flow in
Transfer Enhancement Microscale and
V.G. RIFERT, Thermodistillation, Kiev,
Ukraine and H.F. SMIRNOV, State Nanoscale Structures
Academy of Refrigeration, Odessa, Editors: M. FAGHRI, University of
Ukraine Rhode Island, USA and B. SUNDÉN,
Lund Institute of Technology, Sweden
Professors V.G. Rifert and H.F. Smirnov
have carried out research on heat transfer Presenting state-of-the-art knowledge in heat
enhancement by condensation and boiling transfer and fluid flow in micro- and
for over 30 years and have published more nanoscale structures, this book provides
than 200 papers on the topic. In this book invaluable information for both graduate
they provide research results from the researchers and R&D engineers in industry
former USSR to which there has previously and consultancy. All of the chapters are
been little access and also describe different invited contributions from some of the most
theoretical models of the condensation prominent scientists in this active area of
process. interdisciplinary research and follow a unified
Partial Contents: Theoretical Principles outline and presentation to aid accessibility.
of Heat Transfer at Film Condensation; Contents: Miniature and Microscale
Condensation on Horizontal Low-Finned Energy Systems; Nanostructures for
Tubes – Theoretical Models; Experimental Thermoelectric Energy; Heat Transport in
Study of Condensation Heat Transfer on Superlattices and Nanowires;
Finned Tubes; Condensation on Vertical Thermomechanical Formation and Thermal
Profiled Surfaces and Tubes; Heat Transfer Detection of Polymer Nanostructures;
Enhancement at Film Condensation Inside Two-Phase Flow Microstructures in Thin
Tubes; Condensation in the Electric Field; Geometries – Multi-Field Modeling;
Hydrodynamics and Heat Transfer at Film Radiative Energy Transport at the Spatial
Condensation of Rotating Surfaces. and Temporal Micro/Nanoscales; Direct
Simulation Monte Carlo of Gaseous Flow
Series: Developments in Heat Transfer, and Heat Transfer in a Microchannel;
Vol 10 DSMC Modeling of Near-Interface
Transport in Liquid-Vapor Phase-Change
ISBN: 1-85312-538-5 2004 392pp Processes with Multiple Microscale Effects;
£144.00/US$230.00/€216.00 Molecular Dynamics Simulation of
Nanoscale Heat and Fluid Flow.

Vol 13
All prices correct at time of going to press but
subject to change. ISBN: 1-85312-893-7 2004 392pp
WIT Press books are available through your £117.00/US$187.00/€175.50
bookseller or direct from the publisher.
Transport Phenomena in Thermal Analysis of
Fuel Cells Welds
Editors: B. SUNDÉN, Lund Institute of N.T. NGUYEN, ETRS Pty Ltd., HRL
Technology, Sweden and M. FAGHRI, Services, Mulgrave, Australia
University of Rhode Island, USA
This book is written for postgraduate
This is the first book to provide a students, and welding, mechanical design
comprehensive analysis of transport and research engineers who deal with
phenomena in fuel cells, covering problems such as residual stresses and
fundamental aspects of their function, distortions of welds, design of welded
operation and practical consequences. It will structures, micro-structure modelling of
contribute to the understanding of such welds and optimisation of welding
processes in Solid Oxide Fuel Cells (SOFC), sequences and procedures.
Proton Exchange Membrane Fuel Cells The subject is approached in a simplified
(PEMFC) and Direct Methanol Fuel Cells way, focusing on heat conduction and step-
(DMFC). Written by eminent scientists and by-step derivation of the analytical solutions
research engineers, the chapters focus on using fundamental calculus. Solutions are
various mathematical models and simulations given in closed form and are ready for use
of transport phenomena in multiphase flows. by means of simple integrals, while
Relevant experimental data is also featured. applications are demonstrated through easily
A detailed summary of state-of-the-art accessible case studies.
knowledge and future needs, the text will be Special features include new analytical
of interest to graduate students and solutions developed by the author for
researchers working on the development of various 3D heat sources and a CD-ROM
fuel cells within academia and industry. containing Visual Basic programs combined
into the WHEATSIM (weld heat simulation)
Series: Developments in Heat Transfer, package.
Vol 19
ISBN: 1-85312-840-6 2005 432pp Vol 14
£142.00/US$227.00/€213.00
ISBN: 1-85312-951-8 2004
352pp+CD-ROM
£124.00/US$198.00/€186.00
Find us at
Save 10% when you order from our

encrypted ordering service on the
web using your credit card.
Plate Heat Exchangers Advanced Computational
Design, Applications and Methods in Heat
Performance Transfer VIII
L. WANG and B. SUNDÉN, Lund
Institute of Technology, Sweden and R.M. Editors: B. SUNDÉN, Lund Institute of
MANGLIK, University of Cincinnati, USA Technology, Sweden, C.A. BREBBIA,
Wessex Institute of Technology, UK and
During recent years research into PHEs has A.C. MENDES, University of Beira
increased considerably and there is now an Interior, Portugal
urgent need for a state-of-the-art review of
knowledge on this topic. Heat Transfer topics are commonly of a
Fulfilling this need, this book will enable very complex nature and may involve
graduate students, researchers, and R&D several different mechanisms. Advances in
engineers in industry to achieve a better numerical solution methods of nonlinear
understanding of transport processes. partial differential equations and access to
Partial Contents: Construction and high-speed, efficient computers have led to
Operation; Applications; Materials and dramatic progress in recent years. There is
Manufacturing; Multi-Pass Flow still a need, however, to develop further
Arrangements; Thermal-Hydraulic innovative approaches for the solution of a
Performance in Single-Phase Flows; variety of problems of current interest.
Fouling; Extended Design and Operation Containing papers from the Eighth
Issues. International Conference on Advanced
Computational Methods in Heat Transfer,
Series: Developments in Heat Transfer, this book contains discussion of advanced
Vol 11 topics, new approaches and applications of
advanced computational methods.
ISBN: 1-85312-737-X 2005
apx 350pp Series: Computational Studies,
apx £125.00/US$193.00/€187.50 Vol 5
ISBN: 1-85312-705-1 2004 536pp

£186.00/US$298.00/€279.00
We are now able to supply you with details of new

WIT Press titles via
E-Mail. To subscribe to this free service, or for
information on any of our titles, please contact
the Marketing Department, WIT Press, Ashurst
Lodge, Ashurst, Southampton, SO40 7AA, UK
Tel: +44 (0) 238 029 3223
Fax: +44 (0) 238 029 2853
E-mail: marketing@witpress.com

Jan Szargut - Exergy Method - Technical and Ecological Applications-WIT Press (UK) (2005)

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Jan Szargut - Exergy Method - Technical and Ecological Applications-WIT Press (UK) (2005)

Uploaded by

Copyright:

Available Formats

Exergy Method

Technical and Ecological

C.I. Adderley S. del Guidice

C.A. Brebbia P.J. Heggs

R.M. Cotta D.B. Ingham

G. de Vahl Davies P.S. Larsen

A.J. Nowak D.B. Spalding

P.H. Oosthuizen E. Van den Bulck

For USA, Canada and Mexico

British Library Cataloguing-in-Publication Data

A Catalogue record for this book is available

Library of Congress Catalog Card Number: 2004113017

© WIT Press 2005.

Printed in Great Britain by Athenaeum Press Ltd, Gateshead.

All kinds of human activities are supported by a consumption of natural

Exergy balance and exergy losses

Figure 1.1: Comparison of a hydraulic and thermal power plant.

where T0 = absolute ambient temperature

In comparison to energy (which is a function of the state of the considered

where T0= environmental temperature

diminished without changing the structure or principle of the process. For

1.2. Exergy balance and exergy efficiency

B d = ' B s + 6 ' B q + B a u + B a w +W + G Bi (1.4)

B d = B au + B aw + 6'B q + W + įBi (1.6)

where the dotted terms denote quantities per unit time.

Figure 1.2: Flow diagram of the exergy balance.

Bau  Bdr + 'Bsu + Ȉ'Bqu +Wu

'Bsu= useful exergy increase of the system

Example 1.1. The exergy efficiency of a thermal prime mover can be

where WD = driving work, Qu = useful heat, Tu = the mean temperature of the

Example 1.2. In a complex (multi-purpose) process, the ratio of the energy

where the symbols: see eqns (1.8) and (1.9).

Exergy losses in the individual links are

įB1 = BN (1  ȘB1 ), įB2 = BN Ș B 1 (1  ȘB 2 ), įB3 = BN Ș B 1 ȘB 2 (1  ȘB 3 ) (1.14)

1.3. Exergy and anergy

1.4. Typical irreversible phenomena

where Qf = heat of friction

1.4.2. Irreversible heat transfer

where dQ= elementary amount of transferred heat

Figure 1.6: Temperature distribution and exergy loss in a heat exchanger.

Throttling is a particular case of irreversible adiabatic expansion (the performed

where V is the volumetric flow rate of the fluid.

where n denotes the molar flow rate of the gas.

Diffusion appears in many technical and natural processes. In the simplest

where yi = molar fraction of the ith component

where nx = consumption of technical oxygen, in moles per mole blast, yB = molar

290u8.3143[0.3 ln 0.3+0.7 ln 0.7 – 0.122(0.95 ln 0.95+0.05 ln 0.05)

Combustion is a complex process composed of several irreversible steps:

1.4.6. Absorption and emission of thermal radiation

The absorption of thermal radiation on a solid surface is always connected with

When considering the thermal radiation of a closed surface, the density of

1.5. Anthropogenic and natural exergy losses

¦ 'S = 272 TW / K, į B = 78.500 TW

Exergy of a stream of matter crossing an immovable system boundary (flow exergy)

where V = volume of the considered part of the system

2.2. Physical exergy

bph hph  T0 s ph (2.4)

where hph,sph denote the specific physical enthalpy and entropy.

In the case of ideal gases eqn (2.5a) takes the form

Under the additional assumption of a constant thermal capacity the tempe-

where cp denotes the specific thermal capacity at constant pressure.

In the case of ideal gases the formula becomes:

Figure 2.1: Reduced physical exergy of a perfect gas.

B d = B au + B aw + 6'B q + W + įBi (1.6)

Bau Bdr + 'Bsu + Ȉ'Bqu +Wu

įB1 = BN (1 ȘB1 ), įB2 = BN Ș B 1 (1 ȘB 2 ), įB3 = BN Ș B 1 ȘB 2 (1 ȘB 3 ) (1.14)

where V is the volumetric flow rate of the fluid.

where n denotes the molar flow rate of the gas.

¦ 'S = 272 TW / K, į B = 78.500 TW

bph hph T0 s ph (2.4)

bchq ' r G q ¦ Bchk

bchq 738.6 16.3 19.87 1.5 u 3.97 729.1 kJ/mol

bchq ' f G q ¦ nel bchel

bchq 366.5 609.6 1.5 u 3.97 249.1 kJ/mol.

bchrs RrsT0 ln zrs 0 (2.9)

zrs 0 1.03 u 103 u 0.01 u 135.5 1.4 u 103

bchq 8.3143 u 10 3 u 298 u ln0.0014 =16.3 kJ/mol

HgCl4 , JO3 , K , Li , MoO

1.044 0.016(H/C) 0.3493(O/C)[1 0.0531(H/C)] 0.0493(N/C) O

bch ( H L Lzw )ȕ (bchS H S ) zS bcha za bchw z w (2.22)

bch ( H L Lzw )ȕ bchw z w (2.23)

bchq 752.03 33.97 718.06 kJ/mol

bchi bchi RT0 ln ai (2.26)

bb eb q0 eb 0 (2.27)

B r 4S u 63674402 u 147 74900 TW

G B M (1 KM ) N el 26.4 kW 26.4 kW.

| Wi | H 2 H 1 H 4 H 3 1.08('H wI 'H wII )