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Exergy History
Exergy History
Enrico Sciubba*
Dept. of Mechanical & Aeronautical Engineering
University of Roma 1 “La Sapienza”
Roma, Italy
enrico.sciubba@uniroma1.it
Göran Wall
Independent Researcher
Exergy-SE,
Mölndal, Sweden
gw@exergy.se
Abstract
This paper presents a brief critical and analytical account of the development of the concept
of exergy and of its applications. It is based on a careful and extended (in time)
consultation of a very large body of published references taken from archival journals,
textbooks and other monographic works, conference proceedings, technical reports and
lecture series. We have tried to identify the common thread that runs through all of the
references, to put different issues into perspective, to clarify dubious points, to suggest
logical and scientific connections and priorities. It was impossible to eliminate our
respective biases that still affect the “style” of the present paper: luckily, some of our
individual biases “cancelled out” at the time of writing, and some were corrected by our
Reviewers (to whom we owe sincere thanks for the numerous and very relevant corrections
and suggestions).
The article is organized chronologically and epistemologically: it turns out that the two
criteria allow for a quite clear systematization of the subject matter, because the
development of the exergy concept was rather “linear”.
This work is addressed to our Colleagues who are involved in theoretical research,
industrial development, and societal applications of exergy concepts: if they extract from
this article the idea of an extraordinary epistemological uniformity in the development of
the concept of exergy, our goal will be achieved. The other addressees of this paper are
Graduate Students taking their first steps in this field: in their case, we hope that
consultation of our paper will prompt them to adopt and maintain throughout their career a
scholarly valid method of research, which implies studying and respecting our scientific
roots (the sources) but venturing freely and creatively into unknown territory.
In the Conclusions we try to forecast future developments: this is the only part of the paper
that is an intentional expression of our own views: the previous historical-scientific
exposition is instead based on verifiable facts and accepted opinions.
Keywords: Exergy, maximum work, thermo-economics, cumulative exergy cost, history of
exergy.
2
Notice that for electrical energy and for radiation the notion of “exergy per unit mass” makes little sense. The correct
extension of the definition is clear though in the context of every single application
Int. J. of Thermodynamics, Vol. 10 (No. 1) 3
Therefore, neglecting for the moment e) Any irreversibility in the process is
electrical energy3, for an open system S reflected in a further decrease of exergy
identified by the thermodynamic parameters between the initial and the final state:
T1, p1, µ1, V1, z1 that can interact only with a denoting by ∆sirr,1→2 the irreversible entropy
reference environment B at T0, p0, V0, z0, generation, we have:
and in which the concentration of substance ∆e1→2 =T0∆sirr,1→2 (3)
1 is c0, the specific exergy content, in J/kg, is
a state function given by: f) The reference state B (T0, p0, V0, z0,
c0) is necessary to the definition of exergy:
V12 − V02 for an isolated homogeneous system that
e1 = h1 − h0 + + g ( z1 − z 0 ) +
2 cannot exchange either mass or energy with
(1) any other system, exergy is not defined;
c1
∆g1,0
+ RT0 ln
− T0 ( s1 − s0 ) g) If we consider processes that take
c1, 0 place in finite times (always maintaining the
assumption that they can be represented by a
There are several important
proper succession of quasi-equilibrium
consequences of the above definition:
states), equations 1, 2 and 3 maintain their
a) If the system S is in state “0” (i.e., significance, if all the terms therein are
all of its relevant parameters take the same substituted by their time derivatives;
value as those of the reference environment
h) If a system evolves in the presence
B), its exergy is equal to zero: exergy is a
of a varying environment (long geological
thermodynamic potential, a general measure
timescales, or time- or site dependent
of “difference”, and requires two different
external conditions), its exergy level varies
states for its definition.
accordingly, even if its state does not: this
b) There may be particular means, quite simply, that the maximum
combinations of the values of the work we can extract from the system varies
thermodynamic parameters such that e1 < 0: as well.
the physical significance is that in this case,
to bring the system in equilibrium with the 1.4 A word about notation
reference environment, work must be done Different Authors have adopted wildly
on the system by the environment; different notations: we shall uniformly refer
c) If S proceeds from state 1 to state 2, to the notation provided in the Symbols list
its exergy variation in this process is also a above. Where a different significance has
function of state: been used, we shall identify it case by case.
V12 − V22 2. The Early Beginnings: Carnot & Gibbs
e1 − e2 = h1 − h2 + + g ( z1 − z 2 ) + Work
2
c It is widely recognized today that the
∆g1,0 − ∆g 2, 0 + RT0 ln 1 − T0 ( s1 − s 2 ) exergy concept has its roots in the early
c2 work of what would later become “Classical
(2) Thermodynamics”. If an “exact starting
d) If in the transformation 1→2 some date” must be found, this can only be 1824,
heat Q flows under whatever small but finite when Carnot (1824) stated that “the work
temperature differences) into S, the exergy that can be extracted of a heat engine is
of the state 2 is smaller than that of state 1 proportional to the temperature difference
augmented of the quantity of energy Q: between the hot and the cold reservoir”.4 It
exergy has been destroyed in the process is correct to say that this simple statement
(namely, in the transfer of heat from higher led, 30 years later and after much labouring
to lower temperatures); by Clapeyron (1832,1834), Rankine (1851)
and Thomson (1852) to the position of the
3 4
For the sake of simplicity, and in line with current It is still a matter of debate whether Carnot’s
use, we do not include in Eqn. 1) other contributions, “caloric” ought to be interpreted as “heat flux” or
that may become important in specific applications: “entropy”. The context he uses the word in is often
nuclear, magnetic, molecular vibration exergy, etc. (and clearly unintentionally) ambiguous.
4 Int. J. of Thermodynamics, Vol. 10 (No. 1)
second law of thermodynamics by Clausius of entropy, and though neither of them
(1850,1867). However, Gibbs (1873) who explicitly mentions an availability function,
had earlier defined the thermodynamic it appears that they make a “mental use” of
function “available energy”, was the first to the concept.
explicitly introduce the notion of available Some reflections on Gouy’s work
work, including the diffusion term. He appeared in France due to Jouget, who in a
stated: “We will first observe that an series of works (1906, 1907, 1909), applied
expression of the form the “dissipated work” concept (exergy
-ε + Tη - Pv + M1m1 + M2m2 … + Mnmn destruction in modern terms) to thermal
(4)5 machines. Similar considerations, that imply
a critique of the “first law” efficiency for
denotes the work obtainable by the thermal-to-mechanical conversion processes,
formation (by a reversible process) of a were developed in the US by Goodenough
body of which ε,η,v,m1,m2,…mn are the (1911) and de Baufre (1925), in Germany by
energy, entropy, volume, and the quantities Born (1921) and in France by Darrieus
of the components, within a medium having (1930, 1931) and Lerberghe & Glansdorff
the pressure P, the temperature T, and the (1932).
potentials M1,M2,… Mn. (The medium is In the same years, J. H. Keenan in a
taken to be so large that its properties are series of fundamental works expanded and
not sensibly altered in any part by the clarified the concept of exergy (in his
formation of the body.)” notation, “availability”). His publication “A
Equation 4 (n.54 in Gibbs’ work), is in steam-chart for second-law analysis”
exact correspondence with the present (Keenan 1932) included explicit references
definition of exergy, equation 1 above. to most of the earlier work. His textbook on
thermodynamics (Keenan 1941) has exerted
Tait (1868), and Lord Kelvin as well,
an important influence on his
had also defined in his lectures something
contemporaries, and substantially
similar to Gibbs availability, but offered no
contributed to a more widespread knowledge
extended discussion of the concept. Also
about second law analysis in general and
Duhem (1904) in France and Caratheodory
about the availability concept in particular.
(1909) in Germany elaborated on Gibbs’
“availability”. Contemporary to Keenan, Fran
Bošnjakovic (1935, 1938), a Croatian who
With no direct reference to Gibbs’
taught in Dresden, Zagreb, Braunschweig
work, the Frenchman L.G. Gouy (1889) and
and Stuttgart, laid the foundation of the
the Slovak A. Stodola (1898)6 independently
German school of applied and theoretical
derived an expression for “useful energy”
Thermodynamicists, that were to further
(in French énergie utilisable) as the
develop the concept of exergy two decades
diffeence between the enthalpy and the
later. He published fundamental
product of a reference temperature (which
contributions to the identification of
they specifically stated to be the ambient, or
irreversibilities by a proper Second Law
environment in modern terms, temperature)
analysis, and stressed the importance of
and the change in entropy, To∆S7.
Gibbs’ availability, that he called Work
Maxwell (1871) and Lorenz (1894) Potential (Arbeitsfähigkeit). In the same
presented some applications to the years, additional fundamental contributions
evaluation of thermal processes on the basis were published by Rosin & Fehling (1929),
who calculated the exergy of fuels, Emden
5
Gibbs’ original notation has been maintained here
(1938), and Rant (1947) who provided one
6
Aurel Stodola lived and worked in Switzerland, of the first exergy analyses of a chemical
where he was a professor in the ETH- Zürich process (soda production). Some interesting
7
It is interesting that a paper by Gouy (1889b) was applications of the “available energy”
criticized by Duhem (1889), who claimed priority in concept to the analysis of heat exchangers
the “discovery” of available energy (energìe
utilizable). Gouy rebutted (1889c), but the issue was were published in Russia (Gochstein 1939,
not conceded by Duhem. In modern terms, Duhem Kirpitschev 1949) and in Germany (Glaser
was referring to the Gibbs free energy function (u-Ts), 1949).
and Gouy to exergy (u-T0s): thus, Gouy was right!
Int. J. of Thermodynamics, Vol. 10 (No. 1) 5
In the US, Obert & Birnie (1949), As stated above, the modern definition
published a seminal paper dealing with the of exergy is a rephrasing of Gibbs’ original
assessment of the losses in a fossil fuelled statement: The exergy of a thermodynamic
power plant: the novelty was the use of system S in a certain state SA is the
availability to locate the most critical maximum theoretical useful work obtained if
processes, a theme that will be tackled again S is brought into thermodynamic equilibrium
about two decades later. with the environment by means of ideal
The legacy of those early years is too processes in which the system interacts only
often forgotten: to a modern reader, it is with this environment.
apparent that in all the works quoted above, Baehr gave in 1962 another definition,
the concept of what we now call exergy which is still widely used especially in
analysis was entirely clear to all Authors energy conversion applications: Exergy is
(except perhaps for the very early ones: the portion of energy that is entirely
Carnot, Clapeyron and Clausius). The convertible into all other forms of energy.
problem of the reference state had already (in German, die Exergie ist der
been posed, but was not investigated at all in unbeschränkt, d.h. in jede andere
its implications; the possible effects of a Energieform umwandelbare Teil der
Second Law analysis on the then scarcely Energie). This definition is though
available cost-efficiency correlations was misleading, because it implies that the “total
also well understood; but the emphasis was energy” of a system is composed of two
generally placed on the possibility of additive parts, one “convertible” (exergy)
decreasing the internal process and one non-convertible (anergy)8. But there
irreversibilities and improve the “real are several examples of systems with a
efficiency” of the processes under negative anergy (solids below T0, gases in
examination. certain ranges of T<T0 and p<p0, etc.), and
this makes the use of Baehr’s definition
3. The Definition of the Concept and of Its cumbersome.
Fields of Application: 1950-1970
The mature definition provided above
At a scientific meeting in 1953, the had its roots in fifteen years of intense
Slovenian Zoran Rant suggested that the debate about the exergy concept: this debate
term exergy (in German Exergie) should be took place mostly in Germany, with only
used to denote “technical working capacity” marginal contributions from France,
(Bošnjakovic’s technische Arbeitsfähigkeit). Switzerland, Italy and Sweden. It turns out,
This was the proposal of a cultivated man: that in the same years (1950-1965) some
energy literally means “internal work” (from prominent scientists from Russia and
the Greek en [εν] and ergon [εργον]), and Eastern Europe (Martinowsky 1950,
the prefix ex [εξ] implies instead an Gochstein 1951, 1962, 1963, Martinowsky
“external” quantity. Rant even published & Alexejev 1955, Brodyanski & Meerzon
(1956) a linguistic essay to discuss 1960, Brodyanski & Ishkin 1962,
international equivalent names for this Brodyanski 1963, 1964, 1965, 1967,
quantity (he proposed exergie in French, Andreev & Kostenko 1965, Chernyshevsky
exergia in Spanish, essergia in Italian and 1967) also published fundamental
eksergija in Slavic languages). By adopting contributions to the field: but their works
this name, all previous expressions, such as were not directly available to the larger
available energy, availability, available scientific body of the world, and therefore
work, potential work, useful energy, the two developments remained somewhat
potential entropy, etc. and later introduced independent for years (the only link being
terms such as essergy could in principle be
abandoned. In practice, it took 50 years for
Rant’s denomination to become accepted 8
Baehr (1965) also discussed the function anergy,
worldwide: even at present, some US which we shall not consider here, since it is redundant
Authors still use the obsolete “availability” (anergy=energy–exergy in his definition): but several
terminology. Authors published on anergy to a large extent until
recently (Erdelyi 1952, Almqvist 1964, Szargut 1966,
Geisler 1969, Kalitzin 1969, Kurt 1969, Tuma 1971,
Wachter 1977, Muschik 1978, Alefeld 1988a).
6 Int. J. of Thermodynamics, Vol. 10 (No. 1)
provided by Eastern European scholars who incorporates other thermodynamic concepts
had direct access to the Russian sources). such as Gibbs free energy, Helmholtz free
At first, there was an effort to energy, enthalpy, as well as the
reformulate the thermodynamic problem- “availability” introduced by Keenan. In
solving procedures in terms of entropy or Evans’ mind, even Gibbs free energy,
exergy: thus, Gourdet & Proust (1950), Helmholtz free energy and enthalpy could
Glaser (1953), and Rosin & Fehling (1929), easily -albeit with due attention- be replaced
among others, published enthalpy/exergy or by exergy. The theoretical value of the
enthalpy/lost work diagrams and developed concept of exergy (in his notation, still
process analysis procedures on these bases. “availability”) was addressed by Myron
Then, a major problem that was the matter Tribus in his 1961 MIT course on
of heated debates was the proper definition Thermodynamics: his goal was to unify
of the “efficiency” of a thermal process: in “classical” thermodynamics originating from
the works of Darrieus (1931), Hauser the work of Carnot with statistical
(1950), Hegelmann (1950), Grassmann mechanics and information theory that had
(1950)9, Frieder (1952), Lange (1953), evolved from the atomic model to the new
Schmidt (1953), Grassmann & Kammerer concept of quanta, and to reconcile the
(1954), Kammerer (1954), Nesselmann definitions of entropy. But Tribus’ major
(1955), Bock (1956) and Mattarolo (1956) a accomplishment today is considered to be
critical review of “first law” efficiency the “invention” of Thermo-Economics10, see
definitions leads, on the basis of theoretical below, Section 7.
justifications, to a proposed “new definition” Theoretical developments, mostly
of a Second Law based performance aimed at a systematic analysis of the
parameter. It is noteworthy that this debate efficiency concept, were coupled with
continued in the 1960s’, and led to the practical and often very innovative
modern efficiency definitions we are using applications to the exergetic assessment of
today (see the books by Kotas 1985, Moran both existing cycles and processes in the
1986, Bejan, Tsatsaronis & Moran 1996, works of Almqvist (1964) in Sweden, of
Szargut 2005). In general, the goal of these Andreev & Kostenko (1965) and Brodyanski
Authors is to show that the thermodynamic (1964, 1968) in Russia, of Fratzscher (1961),
performance of any process in which energy Gašperšič (1961), Rant (1961), Gasparovic
is converted from one form into another (1962), Baehr (1962, 1963, 1965, 1968),
cannot be measured properly by First Law Bošnjakovic (1963, 1965), Giesen (1965),
considerations, and that the energy in- and and Heller (1968) in Germany, of Borel
outflows ought therefore to be expressed in (1965) and Berchtold (1970) in Switzerland,
exergy terms. of Chambadal (1965a) in France, of Medici
In the same years, other Authors were (1966) and Codegone (1967) in Italy, of
involved in a theoretical debate about the Gaggioli (1961) and Evans (1969) in the US,
foundation, the formulation and the of Szargut (1954, 1956, 1957) and Petela
applicability of exergy: the list includes (1963) in Poland. These works led not only
among others Keenan (1951), Nesselmann to a more thorough understanding of the
(1952, 1953), Heller (1954), Marchal intrinsic loss mechanisms of engineering
(1956), Denbigh (1956), Elsner & Fratzscher processes, but at times to quantum advances
(1957, 1959), Evans (1958), Fratzscher in cycle configurations, obtained by the
(1959), Ackeret (1959), Bruges (1959), who more accurate analysis of the irreversibilities
all published original contributions to the allowed by the exergy approach.
field, and developed applications mostly in Bošnjakovic (1961) edited a Special Issue of
the field of energy conversion, heat
exchangers and chemical processes. 10
In spite of lack of formal acknowledgement on the
Robert B. Evans (1961) showed that part of Tribus, it is clear in hindsight that he ought at
least to share this credit with El-Sayed and Evans, who
exergy (which he called “essergy”) in itself were working in his group at the time. Both made
fundamental contributions to the field (Evans in the
9
In recognition of Grassmann’s fundamental years 1960-1980; El-Sayed is still active at the time of
contributions to the field, the exergy flow diagrams of this writing). By contrast, Tribus did not publish any
a process are called today “Grassmann diagrams” further on this topic.
Int. J. of Thermodynamics, Vol. 10 (No. 1) 7
the BWK, and Baehr (1965) edited another that in Germany, due to the free exchange of
monography for the German Engineering information within the then Eastern Block.
Society (Verein Deutsche Ingenieure, VDI): At the end of the 1960s’, thus, the
both works contain several interesting and theory of exergy was more or less
seminal papers on exergy analysis. completed, but only a small number of
A mature topic requires a standard practical applications had been discussed
notation system: Szargut (1962, 1964) and (mostly to chemical systems and to energy
later Weingaertner (1969) suggested two conversion plants): in retrospect, we can say
(different!) notational systems. As we shall that in general the intellectual fallout of the
see, this problem with notation was at least exergy theory to industrial applications was
formally solved only much later (Kotas et al. slight if not absent at all.
1987), but these early attempts were
symptomatic: not only a single 4. The Mature Exergy Theory: After 1970
thermodynamic function (exergy) was In our view, the extraordinary
referred to under different names (available development and expansion of the exergy
energy, exergy, maximum potential work, theory in the 1970s’ and the exponential
work capacity), but there were almost as growth of its applications were due to two
many definitions of “exergy efficiency” as very different but equally influential causes:
there were Authors in the field. The dispute one is the concise, clear and stimulating
about the correct name to attribute to the discussion offered by some textbooks of the
function “h-Tos” went on for years, but the 1960s’ (Baehr, Schmidt, Obert,
definitions of efficiency that emerged from Hatsoupoulos & Keenan), that prompted
the debate of the 1960s’ converged to three generations of graduate students in
fundamental ones: Engineering Thermodynamics to enter the
a) the “Second Law” or “exergy” field; and the other is the so-called “oil
efficiency crisis” of 1973, that forced Governmental
Agencies and industries in industrial
useful exergy output
ε= (5) Countries to concentrate on “energy
used exergy input savings”. Increasing the “efficiency” of the
chain of transformations that lead from raw
b) the degree of reversibility
resources to commercial products requires a
exergy of " products"
ψ= (6) thorough understanding of the location and
∑ (exergy inputs) of the relative importance of irreversible
losses, and this is where, of course, exergy
c) the coefficient of exergetic analysis comes to use.
destruction
In fact, most of the theoretical
annihilated exergy publications produced from the beginning of
ξ=
total exergy input the 1970s’ to the end of the 1990s’ (with the
(7) exception of Thermoeconomics, see Section
TO ∆sirr
= 7 below) deal with optimization procedures:
∑ (exergy inputs) the goal becomes that of defining the most
convenient objective function that
This debate about the correct efficiency
maximizes the exergetic yield of a process
definition was very relevant in the European
for a given resource input. Thus, the
literature (Grassmann 1950a,b, Kammerer
problem of correctly identifying the proper
1954, Nesselman 1953, 1955, Bock 1956,
performance indicator for each elementary
1957, Fratzscher 1961, Gasparovic 1962,
transformation or for an entire process is
Nitsch 1964, Borel 1965, Baehr 1968), much
discussed in an extremely large number of
less in the US, where the definitions
publications worldwide. In this period, the
proposed by Keenan (1941), Obert
first international workgroups are organized
(1948,1960) and Obert & Gaggioli (1963)
to facilitate the exchange of information by
were later refined and completed by
forcing different schools of thought to
Gaggioli (1961a, 1968), and almost
confront each other, and this results at once
uniformly accepted in the English literature.
The development in Russia was parallel to
8 Int. J. of Thermodynamics, Vol. 10 (No. 1)
in an extraordinary broadening and Yoshida (1979, 1980), Martinowsky (1979),
deepening of the field. de Nevers & Seader (1979a,b), Sussmann
There is no univocal way to summarize (1979a,b, 1980), Wepfer (1979), Woollert
the enormous amount of work done in these (1979), Yamauchi (1979, 1981), Andrews
years in the field of exergy: we chose here to (1980), Ahern (1980b), Gaggioli (1980,
separately consider theoretical developments 1983), Penner (1980), Silver (1981),
(4.1); theoretical applications to energy Zschernig & Dittmann (1981), Enchelmayer
conservation (4.2) and efficiency (1982), Sato (1982, 1983, 1985, 1986a,b,c),
improvements (4.3); theoretical progress in Wall (1986), Gyftopoulos & Beretta (1987),
chemical processes (4.4); the development Alefeld (1988b,c), Wang & Zhu (1988),
of design tools (4.5); the study of material Zilberberg (1988), von Spakowsky & Evans
properties and of standard reference states (1989a, 1990a,b), O’Toole & McGovern
(4.6); and more tutorial divulgatory works (1990), Lucca (1991), Dunbar et al. (1992),
(4.7). Applications proper (i.e., procedures and Moran & Sciubba (1994), in their works
applied to practical cases) are examined in made fundamental advances in the
Section 5 below. It must be recognized, understanding of the thermodynamic
though, that a substantial degree of meaning of exergy, contributed to a clearer
overlapping exists in most of the references definition of its derivation from prime
quoted here. principles, explained its theoretical
advantages in the analysis of energy
4.1 Theoretical developments transformations, analyzed its correlation
The fundamental analysis and with irreversible losses and with the
development of the exergy concept construction of a measure of an “energy
proceeded at a constant pace in these last 35 quality scale”. Hatsopoulos & Gyftopoulos
years. More and more scholars became (1976a,b,c,d) provided, within a larger
involved in Exergy Analysis, and there is no theoretical framework, a rational derivation
Country which can be regarded as “leading of the "available energy" that is in essence
the field”: though the vast majority of the equivalent to Baehr's maximum work
works listed here were authored by US or concept, but avoids the introduction of an
German researchers, numerous fundamental "anergy" function and extends Baehr's
contributions came from Russia and in maximum work concept, i.e. the “exergy”,
general from the then Eastern Block, from to any system (large or small; macroscopic
Japan and from western Europe. or microscopic, including one-particle
systems) and to any state (stable or not
One of the most debated topics is of stable equilibrium).
course the definition of all the implications
of the exergy function and of its theoretical Ageev & Martynov (1970), Opreschnik
applications: Reistad (1970), Ussar (1970), (1970), Baehr (1971), Brodyansky (1971),
Vlnas (1970), Weingaertner (1970), Alexiev (1973), Martinowsky & Meltser
Wissmann (1970), Thoernqvist (1971), (1973), Martinowsky & Brodyanskyi
Bojadzev (1972), Keller (1972, 1982), (1974), Meltser et al. (1975), Ahern (1980a),
Szargut (1972), Zubarev (1973), Szargut & Maczek (1983) studied the
Chernyshevskyi (1974), Fratzscher (1974), implications of the exergy analysis on
Haywood (1974, 1979), Kalz (1974, 1975, cooling and (Reinke 1971b, Adebiyi &
1976), Medici (1974), Naylor (1974), Russell 1986) air conditioning processes.
Andryuschenko (1975), Mayer (1975), Press (1976), Marshall & Adams
Sawada (1975), Tribus (1975), Yasnikov (1978), Parrot (1978), Karlsson (1982),
(1975), Roegener (1976), Vivarelli et al. Haught (1984), Kutomi & Nobusawa
(1976), Yasnikov & Belousov (1976, (1984), Scholten (1984), Kar (1985), Altfeld
1977a,b), Berchtold (1977), Soerensen et al. (1988), Suzuki (1988a,c), Badescu
(1977a,b), Wachter (1977), Brzustowsky & (1992), Svirezhev & Steinborn (2001),
Golem (1978), Kestin (1978, 1979), Klenke Wright et al. (2002) studied the exergy of
(1978, 1991a,b), Muschik (1978), van Lier solar radiation and/or its implications in the
(1978), Voigt (1978), Andresen & Rubin theory of solar collectors.
(1979), Borel (1979c), Kameyana &
13
The symbol “O” here denotes the initial letter of the Greek word ’όικος (=home) whence all the “eco-” prefixes have
stemmed
20 Int. J. of Thermodynamics, Vol. 10 (No. 1)
9.2 Process structure optimization is identified by a “localised” increase in the
thermo-economical cost-formation chain of
Aceves-Saborio et al. (1989) studied the process: this line of work culminated in
the design optimization of heat exchangers; the so-called “TADEUS” project (a
Aglieri-Rinella et al. (1991) provided an complete TE-Diagnostic procedure with an
exergy-based optimization of a steam application), which was published in 2004
generator for industrial applications; Bejan byValero et al. Though it is true that the
& Siems (2001) applied exergy destruction actual effect of a malfunction can be
minimization to the identification of the correctly measured only by the
quasi-optimal design of an aircraft, corresponding increase in the exergy cost of
considered as an energy conversion system; the output, in our opinion an exergy-cost or
Chinneck (1983) applied a sort of exergy- a TE analysis of a malfunction follows a
enhanced network theory to devise the diagnostic act, and cannot anticipate it. It
optimal structure of some thermal processes; must be remarked though that both Valero
Dekhtyarev (1978) and El-Sayed (2002) and Verda express in their papers exactly the
used an exergy analysis as a guide to opposite opinion.
preliminary design optimization of cyclic
processes, while Doldersum (1998) applied 9.4 Exergy life-cycle assessment
the same approach to identify the optimal This is a line of research that has had
process modifications (revamping) of little momentum since it was proposed by
thermal processes. The important problem of Cornelissen & Hirs (1997), but appears to
optimal synthesis had been discussed deserve more attention as present resource-
previously already by El-Sayed & Gaggioli management strategies move towards
(1988), Evans et al. (1981), Gaggioli et al. “sustainability”. In fact, all the most recent
(1991) and Sama (1995a,b): notice however methods of exergy analysis (including
that an exergy-based approach to the optimal Thermo-Economics, Cumulative Exergy
design of a HEN had been previously Consumption and Extended Exergy
proposed by Pehler (1983). Based on these Accounting) take a life-time perspective,
two latter works, Maiorano & Sciubba and -at least in theory- trace the “exergetic
(2000) and Maiorano et al. (2002) proposed history” of a commodity from well or mine
an exergy-guided intelligent design assistant to final disposal. It is interesting to remark
for Heat Exchanger Networks (HEN). In the that the seed of Cornelissen’s work may be
same line, Monanteras & Frangopoulos found in earlier work by van Gool (1980,
(1999) devised an optimal design procedure 1987) who started as an energy analyst and
for a fuel cell-based powerplant. Szargut only later (van Gool 1990) became an
(2002c) presented a slightly more general exergy practitioner. Cornelissen & van der
formulation for optimal design, which can Berg (2003) extended this line of research
be in principle applied to any process. introducing explicit sustainability
considerations.
9.3 Exergy-based diagnostics
In two seminal works, Torres et al. 9.5 Complex system analysis,
(2002) and Valero et al. (2002) elaborated biological and societal systems
on an original proposal previously made by 9.5.1 Complex Systems: The analysis
Buergel (1974), and developed a method to of complex systems by exergetic methods
identify malfunctions in a component of a consists in the adoption of exergy to express
process by studying their impact on the the energy content of each material or
exergy efficiency of other connected immaterial input- and output stream and of
components. Further work in this area was exergy efficiencies to quantify the system
published by Carraretto et al. (2003). A “performance”. Relevant papers are those of
similar method has been also distilled into Radebold (1974), Le Goff (1977), Morf
an Artificial Intelligence procedure by (1978), Morf (1978), Otoma (1979), Soma
Biagetti & Sciubba (2002, 2004). Lazzaretto (1983), Corliss (1986), Mansson (1986),
& Toffolo (2003), Verda (2003), Verda et al. Malaska & Groenfors (1991), Valero &
(2003), Zaleta et al. (2003) developed a TE- Arauzo (1991), Rosen (1992), Schaeffer &
based diagnostic method, in which the fault Wirtshafter (1992), Özdogan & Arikol
Int. J. of Thermodynamics, Vol. 10 (No. 1) 21
(1995), Sciubba (1995), Connelly & living beings, which by definition are
Koshland (2001a,b), Nikulshin (2001), systems far from equilibrium. The original
Gogus et al. (2002), . works from which such lines of research
9.5.2 Biological Systems: The largest stemmed are those of Knizia (1986) and of
number of publications in this area come course the famous book by Schrödinger
from the “emergy” arena14. The initial idea (1944), both of which were much more
can be traced back to the works of rigorous and did not make recourse to
Joergensen & Mejer (1977, 1981), in which somewhat arbitrary “additional principles of
the Authors proposed to employ exergy as thermodynamics”.
an indicator for biological processes Another line of research was directed to
(emergy had been devised for this purpose a the definition of the modes and methods of
decade earlier). Further refinements of this exergy analysis of complex (networking)
approach were discussed in Joergensen structures, always considered as systems
(1981) and Jizhong et al. (1996). interacting with the Biosphere: Nielsen
Joergensen (1992a, 1992b, 2001, (1995, 1997), Bendoricchio & Joergensen
2004)15, Joergensen et al. (1995, 2002a,b), (1997), Bianciardi & Ulgiati (1998),
Salomonsen & Jensen (1996), Bastianoni & Svirezhev (1997, 2000), Szargut (2003)
Marchettini (1997), Marques et al. (1997), published relevant works in this field.
Xu (1997), Fonseca et al. (2000), Ray et al. 9.5.3 Societal Systems: The first author
(2001), Ray et al. (2001), Debeljak (2002), to explicitly compute the exergy flow
Demirel (2004), Fabiano et al. (2004), Fath diagram of a Nation was Reistad (1975),
& Cabezas (2004), developed several who analysed the US system. The method
applications of an approximate exergy was extended and improved about ten years
analysis of biological systems. Their works later in a much-referenced series of works
are, in our opinion, characterised by a high by Wall (1986, 1990, 2002) and Wall et al.
degree of originality and biological insight, (1994). Societal sectors have also been
but also by a lack of thermodynamic rigor: analysed from a 2-nd Law point of view,
most of their applications rely on both in isolation: Le Goff (1977), Widmer &
equilibrium principles and are applied to Gyftopoulos (1977), Nakicenovic et al.
(1996), Ossebaard et al. (1997), Ptasinski &
14
A discussion of the concept of emergy is beyond the Koymans (2004), and as an integral part of a
scope of this paper. Interested readers may consult the “societal control volume”: Azzarone &
original work by Odum (1970), or the brief and critical
discussion presented in Sciubba & Ulgiati (2005).
Sciubba (1995), Ileri & Gürer (1998),
15 Ertesvag & Mielnik (2000), Ertesvag (2001,
In 1948, C.E.Shannon, then at the Bell
Laboratories, published a paper on information theory, 2004), Mei & Wall (2001), Wall & Mei
A mathematical theory of communication. This was to (2001), Ayres et al. (2003).
be literally the start of a new science, Information The sustainability issue was discussed
Theory. In the context of this review paper, the
importance of Shannon’s work resides in his definition on the basis of an exergy approach by
of an “entropy function” that is depending on the Cornelissen (1997), Kalf et al. (1997),
amount of information bits needed to completely Cornelissen & Hirs (1999), Cornelissen et
define the “state” of a (not necessarily al. (2000) and Cornelissen & Boersma
thermodynamic) system. The implication is obvious:
an exergy value can be attributed to information, or
(2001).
putting it in other words, exergy is a measure of
information content. Similar concepts (using a
9.6 Extended exergy accounting
different definition of entropy) were developed by On the basis of a method developed by
L.Brillouin (1953), and in 1957 E.T.Jaynes published
a formal derivation of Gibbs’ results using Shannon’s
Sciubba (1998), which may be traced back
entropy as a starting point. Though the matter is far to an idea published much earlier by
from being clear in all of its implications, we prefer to Grubbstroem (1985), a new field of exergy
adopt Kline’s point of view here (Kline 1999): he analysis has emerged under the name of
found some fundamental faults in the extension of Extended Exergy Accounting (“EEA”). The
Shannon’s entropy to classical Thermodynamics that
invalidate the equation entropy=information (NOT the method is a standard exergy analysis in
concept: just the dimensional equivalence). There are which Szargut’s CEC (see Section 7 above)
other ways to link exergy to information content, as is augmented by additional exergy flows that
we shall discuss in Section 11 below. represent the exergetic equivalents of the
22 Int. J. of Thermodynamics, Vol. 10 (No. 1)
Capital, Labour and Environmental on Exergy analysis and Thermo-economics,
Remediation Production Factors (whence and finally, the two books by Szargut
the name “extended”): the final “balance” is (Szargut et al., 1988, and Szargut, 2005)
given by an equation formally identical with constitute essential (albeit advanced) reading
eqtn. 8 above. Both in its method and in its for both fundamental theory and
formalization, EEA is very similar to applications.
Valero’s Structured Cost Theory (Section 8),
though there are some non negligible 11. Review Papers, Nomenclature
differences in the form of the Transfer Definitions and Bibliographies
Function Matrix Π. Applications have been The first review paper on exergy was
published by Milia & Sciubba (2000), Belli published by Gasparovic (1961) and -almost
& Sciubba (2001), Sciubba (2001, 2002), concurrently- by Bosnjakovic ed. (1961): for
Ertesvag (2003), Ptasinski & al. (2004). obvious reasons, both included rather few
publications. Later reviews worth
10. Books mentioning are those compiled by Szargut
There are several books that treat (1964), which includes several useful and
exergy in a (more or less) monographic difficult to find references to works
sense. The list provided here is probably the published by Authors in the then Eastern
most complete and updated reference Block; by Baehr ed. (1965) and by Soma
available today. Exergy researchers are (1983), who presented a relatively small list
advised to carefully consult these of references and is rather limited in his
monographs, which offer different and often selection criteria. Another useful source was
contrasting definitions and approaches, but the ACS Symposium Series 235 edited by
definitely provide an enlightening view of Gaggioli (1983). The most comprehensive
the development of the exergy concept reference list (before the one attached to this
through the years. paper) is that compiled by Wall (1987),
The old works by Maxwell (1871), Tait which is very extensive even if not always
(1868), Jouget (1909) and Goodenough precise. Other lists were published by Kotas
(1911) are only of historical interest today. et al. (1987); by Elsner (1993), which is
Interesting are the early developments more a historical overview of the theory and
presented by Bosnjakovic (1935) and concepts than a real review paper; by
Keenan (1941), this second one with Cornelissen (1994) in his Ph.D. dissertation;
fundamental applications that are still by Kay (1989, placed on the web in 1998);
relevant after over 60 years. Also and by Rezac & Metgalchi (2004), who
fundamental are the two books (in German) approached the subject from a more
by Schmidt (1953) and Baehr (1962) that theoretical viewpoint, privileging concepts
have influenced two or three generations of rather than completeness.
european researchers in the field. Other 12. What Next? A (Biased) Look Into the
books on exergy are those of Martinowsky Future
(1950), Gourdet & Proust (1950), Marchal
(1956), Bruges (1959) and Ford et al. To foretell “whereto exergy analysis is
(1975). going” is a double-edged argument:
furthermore, the present authors are
More modern approaches are presented obviously rather strongly biased towards
by Ahern (1980), Kotas (1985) (which is a “Complex Systems” issues, and this might
recommended first lecture for graduate have influenced our conclusions here below.
students in the field), Moran (1982) (very However, with the obvious caveat that such
detailed and tutorial, also a recommended a prediction has to be taken with care, we
lecture), and Sussman (1980). The two can conclude that:
works by Bejan (1982, 1988) are less
monographic and contain a substantial 1) It is clear that Process Analysis will
portion of fundamentals, presented and see more and more applications of Exergy
discussed with a very original approach. The methods. The present ever increasing
later monographic work by Bejan et al. number of publications in the field of
(1996) is presently the most referenced book organic- and inorganic Chemical Processes
is a sure sign that accounting for real process
Int. J. of Thermodynamics, Vol. 10 (No. 1) 23
irreversibilities provides a better grasp of systems still require excessive
even complex processes such as distillation, computational resources for their
petroleum cracking, etc. “optimization”. Notice that since the goal of
In the Energy Conversion arena, there system synthesis is the minimization of the
is today practically no process- or cycle “product cost” (monetary or exergetic), the
analysis that does not include exergy costing functions can be conveniently
considerations. This can be regarded as a expressed by the methods of
very mature field, and it seems that the Thermoeconomics, Cumulative Exergy
exergy methods are on their way to being Content and Extended Exergy Accounting.
regarded as standard industrial analysis Thermoeconomics seems to be the one that
procedures. There are still issues that need to is more likely to be used in practical
be addressed in more depth and breadth, applications in the near future, EEA being a
even at fundamental level: life-cycle exergy good but rather distant second. Interesting
analysis of real processes, the influence of are also some attempts based on heuristics
dynamic operation, the analysis of Very (like the search for an optimal geometry of a
Large Complex Systems are examples. But gas turbine blade, or similar CFD-based
we cannot detect theoretical hindrances on exergy destruction calculations, see next
the way of constant advances and point here below), that show potential of
refinements of both theoretical and being transformed into automated -albeit
application-oriented exergy analysis. extremely computationally intensive-
procedures.
Exergy-based optimization procedures
exist, and more will undoubtedly be 4) It is possible, and highly desirable,
developed in the future. A present limit here that the application of exergy methods be
is posed by the immense computational expanded into the realm of thermo-
resources required by a complete fluiddynamics applications. Under the
optimization of systems with a high number continuum hypothesis, the local entropy
of relevant parameters (each one of which generation rates can be computed by most
constitutes a degree of freedom for the present CFD codes, and therefore the exergy
optimization). destruction in heat- and fluid flow can be
properly assessed even at local level: this
2) It is also rather clear that Thermo- may lead to the concoction of more effective
Economic methods will be more and more design methods for fins, compact heat
extensively adopted in the assessment of exchangers, ailerons, surface treatment
industrial processes and production cycles. and/or injection/suction, etc. This is an area
There are still some issues as to the in which not much has been published to the
inclusion of environmental considerations date of this writing (see though Bejan 1982,
into TE, and some major research effort is Carrington & Sun 1992, Fewell et al. 1981,
needed in this area, because the presently Harrison & Dean 1978, Kouremenos 1971,
proposed solutions are not entirely Natalini & Sciubba 1994 & 1999,
satisfactory. Poulikakos & Bejan 1982, Sciubba 2004),
3) System synthesis is most likely the but which might open up entirely new
“next frontier”: the possibility of perspectives as energy (exergy!) efficiency
formulating an optimization problem in becomes a more important issue.
which the independent variables are not only 5) The interconnection of the exergy
related to process parameters but also to concept with “environmental issues” (taken
process configuration is very real already at in their broader sense) is also likely to be
present: at least formally, the problem can explored in more depth. Exergy per se is
be solved by MILP techniques (Muñoz & NOT a measure of environmental impact,
von Spakovsky 1999), Genetic Algorithms but in essence at the end of the life cycle of
(Toffolo & Lazzaretto 2002), and Artificial any device, plant and product, the exergy
Intelligence techniques (Melli et al. 1992, “balance” of the extraction-transformation-
Sciubba & Melli 1998). Practical production-distribution-use-disposal cycle
applications to simple systems (i.e., systems shows how many primary exergy resources
with few independent variables) have have been actually used up (consumed), and
already been published. Large complex there are already some studies that address
24 Int. J. of Thermodynamics, Vol. 10 (No. 1)
the issue of designing “more exergy- (see Section 4.1 above) Hatsopoulos and
conscious” production cycles to attain a Gyftopoulos argue against this view, and
higher degree of sustainability. propose an extension of the definition of
6) In a closely related field, namely the exergy that applies also to microscopic non-
analysis of “living” systems, we are not so equilibrium systems. In our opinion, the
optimistic. Exergy is a thermodynamic issue awaits clarification, and some
function defined for equilibrium or quasi- additional research is definitely needed in
equilibrium processes, and its extension to this field.
far-from-equilibrium systems (as all living 9) The few attempts to define “the
systems are) is not to be taken for granted. exergy content of one bit of information”
Thus, unless some breakthroughs in (based on mind-experiments performed on
irreversible thermodynamic are made, we boxes and “pistons” with 1, 2 or 3 atoms)
neither foresee nor favour exergy analyses strongly suffer from a lack of well-founded
of plants, forests, bacterial colonies and the theoretical development. Notice that in their
like, and much less those of human beings. above quoted works, Hatsopoulos and
In some living systems analyses, the Gyftopoulos (1976a,b,c,d) argue quite
use of an “information exergy” is proposed. strongly from a theoretical and mathematical
This exergy is considered to correspond to standpoint that such an informational
the genetic “information” contained in the framework contains a built-in violation of
DNA. We must remark that a) there is no the 2nd Law. A more formal critique has
proven link between exergy and information been raised by Kline (1999, see footnote #15
except in a strictly physical sense specified on previous page). We must stress that in
under point 7 here below, and b) our view the only reasonable way to account
“thermodynamics of life” -if such an object for information is at present a CEC or an
exists!- goes well beyond the concept of EEA approach, in which the amount of
“transmitting information”. physical resources expended for the
generation of 1 bit of information can
7) Cumulative Exergy Consumption actually be computed on the basis of an
methods are likely to see more and more analysis of the process that generates this
applications in the near future. They provide bit: also this view is, of course, in dispute.
an extremely clear picture of the “resources”
used up (incorporated in) the production of 10)On the opposite, an application of
goods. They can be extended to include exergy analysis to macroscopic physics
immaterial services, and (like in EEA) they (astronomy, for instance) appears possible,
can account for labour and capital as well, even if no example is known to us as of
thus paving the way to the calculation of an 2004 except for Jørgensen et al. (1998).
“exergy cost” of commodities measured in Since exergy includes both gravitational and
kJ/unit (as in CEC and EEA) instead of €/kJ radiation effects, it is in principle possible to
(as in Thermo-Economics). An open perform an exergy “balance” of a galaxy
problem for CEC is its neglect of Labour (the "reference environment" being the 3K
and in general of all immaterial production residual radiation field). Far fetched as it
factors; but this issue is being already may seem, such an analysis might lead to
debated in the literature, and it is likely that interesting finding on the entropy generation
a satisfactory solution can be found. This rate of the Universe.
would be good news, because there are List of Symbols
numerous proposed applications to the
analysis of societal systems that could B Reference system, Biosphere
greatly benefit from the existence of an c Molar concentration
accepted paradigm. cp Specific heat, J/(kg K)
e Exergy, J/kg
8) Application of exergy analysis to
g Gravitational constant, m/s2
microscopical physics appears problematic.
gG Gibbs free enthalpy, J/kg
The current paradigm prescribes that, once
h Enthalpy, J/kg
either the continuum and/or the equilibrium
I Electric current, A
hypothesis are abandoned, exergy becomes a
IR Radiative energy flux, W/m2
matter of convention. In their 1976 work
Int. J. of Thermodynamics, Vol. 10 (No. 1) 25
q Specific thermal energy, J/kg Suffixes
R Gas constant, J/(kg K)
0 Reference conditions
s Entropy, J/(kg K)
irr Irreversible
t Time, s
T Absolute temperature, K References
u Internal energy, J/kg
V Velocity w.r.t. Galilean frame, m/s The present paper contains over 2600
w Specific work, J/kg references: it was clear from the onset that it
z Elevation, m would have been impossible to include a
regular “Reference List”. We decided
Greek symbols instead, with the permission of the IJoT
Editor, to attach here a link to the Journal
∆V Electrical potential, Volts web-site where the cited works are properly
ε Exergy efficiency listed. We will be grateful to readers who
η Energy efficiency suggest additions or corrections to this list.
µ Chemical potential, J/kg
σ Stephan-Boltzmann constant, W/(m2K4)
ψ Degree of irreversibility www.icatweb.org/vol10/10.1/Sciubba-
ξ Coefficient of exergetic destruction Wall.pdf