7

Chemical Exergy

In the last chapter the concepts of exergy and physical exergy, in particular,
were introduced. This chapter deals with three other important concepts—
namely, exergy of mixing, chemical exergy, and cumulative exergy con-
sumption—and their numerical evaluation.

1 INTRODUCTION

Recall that exergy values reflect to which extent a compound or mixture is out
of equilibrium with our environment. Examples are differences in pressure and
temperature with the environment. Differences in temperature lead to heat
transfer, while differences in pressure lead to mass flow. Chapter 6 shows that
the physical exergy represents the maximum amount of work that can be
obtained from a system by converting a system’s pressure and temperature to
those of our environment.
It appears, however, that when a system’s physical exergy is zero and thus
the system prevails in a state of thermomechanical equilibrium with the
environment, it may still be out of equilibrium with that environment in other
respects. The origin is to be found in the difference in the composition and
nature of the components making up the system and the environment,
respectively. These differences lead to values for the exergy of mixing and the
chemical exergy. Earlier we pointed out that though the physical exergy of
methane is zero, its chemical exergy is not. Equally, pure nitrogen and oxygen
have nonzero chemical exergies because their mole fraction in the environment
is different from 1. Because the process of mixing plays an im-portant role in
the determination of the chemical exergy, the next section deals with the exergy
of mixing.
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2 EXERGY OF MIXING

To clarify the concept of the exergy of mixing, we give the example of pure
oxygen at ambient conditions P0 and T0. Consider a system, for convenience
chosen at P0, T0, isolated from the environment and consisting of two separate
compartments containing oxygen and air, respectively. The two compartments,
initially separated by an elastic diathermal barrier, and thus in mechanical and
thermal equilibrium, are brought in contact with each other by removing the
barrier. Oxygen and air will diffuse into each other, and eventually an
equilibrium will be reached where oxygen and air have mixed into a
homogeneous mixture. The initial condition of oxygen is apparently not one of
complete equilibrium with the environment (i.e., with air) despite the equality in
pressure ( P0) and temperature (T0). The thermodynamic potential of pure
oxygen is higher than that of oxygen in air at P 0 and T0. On mixing of the
components of air in their pure state to a homogeneous mixture, the
thermodynamic potential of each component decreases. The associated change
in exergy is

DmixEx ¼ DmixH T0DminS ð1Þ

As the mixing process takes place at P0, T0, we may write

Ex G ð2Þ
Dmix P0T0 ¼ Dmix P0T0

For the calculation of the exergy value at P, T of a mixture, of a given

composition, with respect to the exergy values of the pure components at P and
T, the exergy difference is defined as

ExmixuDmixEx ð3Þ

with values for DmixH and DmixS at the conditions P and T. Chapter 10 presents
an example of the industrial distillative separation of the mixture of
propane and propene, in which the exergy of mixing is very prominent.

3 CHEMICAL EXERGY

For the determination of a compound’s chemical exergy value we need to define

a reference environment. This reference environment is a reflection of our
natural environment, the earth, and consists of components of the at-mosphere,
the oceans, and the earth’s crust. If, at P 0 and T0, the substances present in the
atmosphere, the oceans, and the upper part of the crust of our earth are allowed
to react with each other to the most stable state, the Gibbs
Copyright © 2004 Marcel Dekker, Inc.
energy of this whole system will have decreased to a minimum value. We then
can define the value of the Gibbs energy for a subsystem, the ‘‘reference
environment’’—at sea level, at rest, and without other force fields present than
the gravity field—to be zero as well as for each of the phases present under
these conditions. It is a logical extension of these assumptions to define the
thermodynamic potentials of each of the substances present in the di fferent
phases to have a value of 0 J/mol. With respect to this ‘‘reference environment,’’
we then determine the thermodynamic potentials of all kinds of substances in all
kinds of phases at P and T. From this ‘‘reference environment’’ it is not possible
to obtain any work. Therefore, this state is also meaningful as a reference state
for the determination of exergy values at P 0 and T0. This finally leads to the
definition Exi ( P0, T0) u Ai ( P0, T0) for the subsystem at sea level, at rest, and
without the presence of any other force field than the gravity field. The concept
of this ‘‘reference environ-ment’’ is illustrated for a number of the so-called
reference components.

3.1 Reference Components from Air

Apart from differences in chemical concentration, or better, thermodynamic
potentials, such as for oxygen, there can be other situations for being out of
equilibrium with the environment at P0, T0. Consider, for instance, the material
graphite. Graphite can spontaneously react with oxygen to from carbon dioxide,
but for kinetic reasons the reaction is very slow and graph-ite seems to be stable
in our environment, although in the presence of oxy-gen it is metastable with
respect to carbon dioxyde. As a result, it has a significant amount of chemical
exergy available and can be considered as an important energy carrier because it
is highly out of equilibrium with the environment.

In our environment there are many substances that, like oxygen in our
atmosphere, cannot further diffuse and/or react toward more stable config-
urations and may be considered to be in equilibrium with the environment.
Neither chemical nor nuclear reactions can transform these components into
even more stable compounds. From these components we cannot extract any
useful work, and therefore an exergy value of 0 kJ/mole has been assigned to
them. This has been done for the usual constituents of air: N 2, O2, CO2, H2O,
D2O, Ar, He, Ne, Kr, and Xe at T0 = 298.15 K and P0 = 99.31 kPa, the average
atmospheric pressure [1]. Their partial pressures Pi in air are given in Table 1.
From these data we can calculate the, chemical, exergy values of these
components in the pure state at P 0 and T0. Air at these conditions can, to a good
approximation, be considered as an ideal gas, therefore, separation into its
constituents will take place without a heat effect: DsepH = 0. And so
Copyright © 2004 Marcel Dekker, Inc.
Table 1 Partial Pressure of Various Components in Air
Component Pi (kPa) Component Pi (kPa)
N2 75.78 He 0.000485
O2 20.39 Ne 0.00177
CO2 0.0335 Ar 0.906
H2 O 2.2 Kr 0.000097
D2 O 0.000342 Xe 0.0000087

the only effect left in the exergy change of separation, DsepEx = Exmix [see
Eq. (3)], is that of the entropy of separation:
DsepEx ¼ DsepH T0DsepS
ð4Þ

¼ T0DmixS
As we recall from Chapter 2, the change in entropy associated with taking one
mole of an ideal gas isothermally from pressure P1 to a pressure P2 is given by
 P
DS ¼ Rln 2 ð5Þ
P1
From this equation we can show [2] that the standard chemical exergy at P 0 and
T0 of a pure component can be calculated from its partial pressure P i in air with
Eq. (6):

Exch
0
;i ¼ RT0ln P0 ð6Þ
Pi
The standard chemical exergy values for the main constituents of air as listed in
Table 1 are given in Table 2.

Table 2 Standard Chemical Exergy Values at P0,T0 of Various

Components Present in Air
Component Exch0 (kJ/mol) Component Exch0 (kJ/mol)
N2 0.72 He 30.37
O2 3.97 Ne 27.19
CO2 19.87 Ar 11.69
H2 O 9.49 Kr 34.36
D2 O 31.23 Xe 40.33

Copyright © 2004 Marcel Dekker, Inc.

 Exergy values for the elements in their stable modification at T 0 = 298.15
0
K and P0 = 101.325 kPa are called standard chemical exergy values Ex ch . For
the calculation of the chemical exergy value of all kinds of substances, the
standard chemical exergy values of all elements are required.

3.2 Exergy Values of the Elements

The following example for graphite illustrates how the chemical exergy value
for all other elements can now be calculated (Table 3). For the calculation of
0
Exch of graphite, we make use of the reaction in which CO 2 is formed from the
elements in their stable modification at P0, T0:
Cðgraphite; sÞ þ O2ðgÞ ! CO2ðgÞ ð7Þ
Table 3 Standard Chemical Exergy Values of the Elements [1]

Element Ex0ch (kJ/mol) Element Ex0ch (kJ/mol)

Ag (s) 70.2 Kr (g) 34.36
Al (s) 888.4 Li (s) 393.0
Ar (g) 11.69 Mg (s) 633.8
As (s) 494.6 Mn (sa) 482.3
Au (s) 15.4 Mo (s) 730.3
B (s) 628.5 N2 (g) 0.72
Ba (s) 747.7 Na (s) 336.6
Bi (s) 274.5 Ne (g) 27.19
Br2 (1) 101.2 Ni (s) 232.7
C (s, graphite) 410.26 O2 (g) 3.97
Ca (s) 712.4 P (s, red) 863.6
Cd (sa) 293.2 Pb (s) 232.8
Cl2 (g) 123.6 Rb (s) 388.6
Co (sa) 265.0 S (s, rhombic) 609.6
Cr (s) 544.3 Sb (s) 435.8
Cs (s) 404.4 Se (s, black) 346.5
Cu (s) 134.2 Si (s) 854.6
D2 (g) 263.8 Sn (s, white) 544.8
F2 (g) 466.3 Sn (s) 730.2
Fe (sa) 376.4 Ti (s) 906.9
H2 (g) 236.1 U (s) 1190.7
He (g) 30.37 V (s) 721.1
Hg (1) 115.9 W (s) 827.5
I2 (s) 174.7 Xe (g) 40.33
K (s) 366.6 Zn (s) 339.2
Copyright © 2004 Marcel Dekker, Inc.
 The corresponding change in standard Gibbs energy is called the standard
0
Gibbs energy of formation of CO2, Df G 298.15, and is defined as
X
Df G0 : u riA0i; : ð8Þ
298 15 298 15

in which ri is the so-called stoichiometric coefficient, defined as positive for

0 0
products and negative for reactants, and A i = Gi is the standard thermo-
dynamic potential or Gibbs energy for substance i. Equation (8) is based on the
formation of 1 mole of the compound considered, in this instance 1 mole of
CO2. If we define the change in exergy in the same way:
Ex 0 G 0 X riAi
0
;298:15
ð9Þ
Df 298 :15 ¼ Df 298 :15 ¼ i

X 0
u riExch ;i
then the exergy of graphite can be calculated from
Ex 0 G 0 1 Ex 0 1 Ex 0 ð10Þ
ch ;CðsÞ ¼ Df 298 :15 þ ch ;CO2ðgÞ ch ;O2ðgÞ
0
The values of Df G298 .15 for many compounds are listed in standard tables [2],
and the value for CO2 reads 394.359 kJ/mole. With the help of Table 2, which
gives the standard chemical exergy values for CO2 and O2, Equation
0
(10) allows the calculation of Exch,C(s) = 394.359 + 19.87 3.97 = 410.26
kJ/mole.
For the remaining elements, reference compounds have been chosen, as
they occur in seawater or in the lithosphere, the earth’s crust. An important
aspect of this choice has been that the calculated exergy values of most
compounds should be positive. Table 3 lists the standard chemical
exergy values of the elements as presented in Szargut’s well-known standard
work [1]. Chapter 8 gives an example, the adiabatic combustion of H 2, to
illustrate the use of these exergy values in an interesting application.

3.3 Chemical Exergy Values of Compounds

Table 3 is useful for the calculation of the standard chemical exergy values of
compounds. We illustrate this for methane and start from its hypothetical
formation reaction at standard conditions:
CðsÞ þ 2H2ðgÞ ! CH4ðgÞ ð11Þ
Applying Eq. (9) results in
Ex 0 G 0 Ex 0 2Ex 0 ð12Þ
ch ;CH4ðgÞ ¼ Df 298 :15 þ ch ;CðsÞ þ ch ;H2ðgÞ

The first term on the right-hand side of this equation is the standard Gibbs
energy of formation of methane, which is listed [2] as 50.460 kJ/mole and
Copyright © 2004 Marcel Dekker, Inc.
 0
thus Ex ch,CH4(g) can be calculated to be 831.6 kJ/mole. Chapter 9 illus-trates the
use of this exergy value in the analysis of a natural gas-driven
powerstation.
In general, we can calculate the standard chemical exergy of a com-
ponent j from the standard chemical exergy of its elements with the equation
0 0
X 0
Ex ;j ¼ Df G j; : þ viEx ;i ð13Þ
ch 298 15 ch

We recall that the exergy of methane will be different for other values of P
and T than P0, T0 and refer to Table 1 of Chapter 6 to demonstrate the influence
of pressure and temperature on this exergy value. It is clear that
0
the chemical contribution to the total exergy, Ex = Ex phys + Ex ch, in this case is
dominant. At the same time we should be aware that in a simple compression
step this contribution is irrelevant and should not be included in an exergy
efficiency calculation. On the level of, let us say, 10 kJ/mole of physical exergy,
the loss of 2.5 kJ/mole of exergy due to inefficiencies of the compressor results
in a thermodynamic or exergetic efficiency of 75%. Had we included the 832 kJ
of chemical exergy of methane, the thermodynamic efficiency would have been
as high as 99.7%, which gives a completely blurred picture of the compressor’s
performance.
Finally, Table 4 gives the standard exergy values of a selected number of
compounds that are relevant for the examples and topics presented in this book.

Table 4 Standard Chemical Exergy Values of

Selected Compounds

Substance kJ/mole
CH4 (g) ‘‘natural gas’’ 832
CH3OH (g) 722
CH3OH (l) 718
UCH2Ua ‘‘oil’’ 652
(CH2O)b ‘‘biomass’’ 480
CO2 (g) 20
SiO2 (s, a quartz) 1.9
TiO2 (s, rutile) 21.4
Al2O3.H2O (s) ‘‘bauxite’’ 200.8
Fe2O3 (s) ‘‘haematite’’ 16.5
NH3 (g) 337.9
CO(NH2)2 (s) urea 689.0
a Crude oil on a per-carbon basis.
b Biomass (glucose) on a per-carbon basis.
Copyright © 2004 Marcel Dekker, Inc.
3.4 The Convenience of the Chemical Exergy Concept
In chemical thermodynamics the reference components have been selected as
the elements in their most common state at standard conditions, the standard
state. These elements have been defined as having a zero standard Gibbs energy
of formation. The standard Gibbs energy of formation of a compound is related
to that of the elements from which it has been composed. Let us take liquid
methanol, CH3OH [1]. Its standard Gibbs energy of formation is 166.270
kJ/mole, a number that does not say very much other than that in the reaction

CðsÞ þ 2H2ðgÞ þ 1 ðgÞ ! CH3OHð1Þ ð14Þ

O
2 2

the standard Gibbs energies at the left-hand side are zero and the standard Gibbs
energy of reaction is also 166.270 kJ/mole. However, following the procedures
as outlined in the above sections, we can calculate with Eq. (13) the standard
chemical exergy of liquid methanol to be 166.270 + 410.26 + 2 236.10 + 1/2
3.97 = 718.2 kJ/mole. This number is very meaningful, as it expresses the
maximum amount of work available to us embodied in one mole of liquid
methanol. We can then compare this with the value for methane and notice that
the partial oxidation of methane to methanol has lowered the exergy value
somewhat, from 832 kJ/mole to 718 kJ/mole. But methanol is in the liquid state,
and this is an attractive feature for a transportation fuel. On the other hand,
methanol has double the mass of methane, and so per unit of mass its available
work or exergy is less than half. And last but not least, the e fficiency of
converting methane into methanol may be about 50–60% (see Chapter 14) and
much of the advantage of using methanol seems to have gone. Nevertheless,
although, strictly speaking, the concept of exergy does not add anything in the
fundamental sense, it certainly adds convenience—for example, for the
discussion on the pros and cons of energy conversion such as in the above
comparison of methane and methanol. This is one of the attractive features of
the exergy concept that has made it so popular with many practitioners.

4 CUMULATIVE EXERGY CONSUMPTION

Suppose we deal with a process in which iron, Fe, has to be used as a reactant,
for example in a reduction reaction. The standard chemical exergy of Fe is
376.4 kJ/mole. If we wish to carry out a thermodynamic or exergy analysis of
this process, this value is not appropriate. After all, to put the exergy cost of the
product, for which Fe was needed as a reactant, in proper
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perspective, we need to consider all the exergetic costs incurred in order to
produce this product all the way from the original natural resources—iron ore
and fossil fuel in this example. The production of iron from, for ex-ample, the
iron ore haematite and coal has a thermodynamic efficiency of about 30% [1],
and therefore it is not 376.4 kJ/mole Fe that we need to consider but 376.4/0.3 =
1250 kJ/mole Fe. This value is called the cumu-lative exergy consumption
(CExC) of Fe. It may well be that for proper analysis of the e fficiency of the
step consuming Fe to produce the product, we want to take the standard
chemical exergy of Fe, but for the calculation of the CExC of the final product,
we need to include the CExC of Fe. Chapter 14 discusses many examples where
the exergy of the final product is compared with the CExC of the same product.
Together these two values allow the calculation of the thermodynamic,
exergetic, efficiency of a process yielding the product from natural resources.
This is part of the subject of Chapter 14.

We recall that, without mentioning it, we touched upon the topic of

cumulative exergy consumption before. In Chapter 6 we illustrate the
application of the concept of physical exergy with the simple example of mixing
liquid water of 100jC with that of 0jC. In that example we first take the exergy
value of hot water as 34 kJ/kg. But when this water has been produced from
natural gas, its accumulated exergy consumption is calcu-lated according to
Table 2 of Chapter 6 to be 1/0.12 34 = 283 kJ/kg.
Finally, we consider another important contributor to the CExC of a
product. We refer to the equipment being used in the process. This equip-ment
also has to be manufactured from resources originally taken from the
environment. This cumulative exergy consumption has to be discounted over
the lifetime of this equipment and then added as a contribution to the
cumulative exergy consumption of the product. Our experience is that this
contribution is negligible for equipment that works continuously. For equip-
ment performing with an irregular operation such as a laundry machine at home,
this contribution may be substantial and makes up a large part of the total
exergy cost of the product.

5 CONCLUSIONS

The concept of chemical exergy has a distinct advantage over the standard
Gibbs energy of formation. Whereas the latter is zero for the elements at
standard conditions, the chemical exergy has a zero value for compounds or
elements in equilibrium with and as they occur in our natural environment. Thus
the standard chemical exergy of a compound clearly represents the amount of
work available with respect to the environment in which we live
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and work. The chemical exergy can be simply calculated from the Gibbs energy
of formation. The only difference between the two concepts is that their zero
values are defined for different reference substances.
The chemical exergy of a molecule in a mixture is smaller than in its pure
state, as it will require work to separate the mixture in its pure constituents, the
exergy of separation. This exergy will be lost as the exergy of mixing when the
pure constituents spontaneously form the mixture. The total exergy of a pure
compound or element is therefore composed of three contributions: the
chemical exergy; the exergy of mixing, and the physical exergy. The last
element accounts for the fact that the molecule may be at different conditions of
pressure and temperature than those of the environ-ment, P0 and T0.

The concept of cumulative chemical exergy consumption is very useful

and accounts for the fact that when a compound (e.g., ammonia) is introduced
into a process, its chemical exergy has to be corrected for the exergy
consumption accumulated since this compound was manufactured from its
natural constituents (air and natural gas in the case of ammonia).
If the thermodynamic efficiency of a process step is calculated, the
chemical exergies should be excluded from the calculation if the process step
does not include chemical conversions. If it does, it may be appropriate to
distinguish between the physical and the chemical efficiency, Dphys and Dchem,
of the process step.
Finally, although the exergy concept is not strictly necessary for the
calculation of the available work lost in the process, it is an extremely handy
tool to calculate losses and efficiencies and for making a quick assessment of
process options. Chapter 8 gives some simple illustrations, whereas Part III,
Case Studies, presents the results of integrated studies in the world of energy
and chemical technology.

REFERENCES

1. Szargut, J.; Morris, D.R.; Steward, F.R. Exergy Analysis of Thermal, Chemical, and
Metallurgical Process; Hemisphere Publishing Corp.: New York, 1988.
2. Smith, J.M.; Van Ness, H.C.; Abbott, M.M. Introduction to Chemical Engi-neering
Thermodynamics, 5th ed.; McGraw-Hill: New York, 1996.
Copyright © 2004 Marcel Dekker, Inc.