Chapter 3

Chemical Exergy
Chapter Outline
3.1 Introduction 31 3.6.1 Chemical Exergy Variation with Temperature
3.2 Chemical Exergy Definition 32 and Moisture Content 41
3.2.1 Standard Chemical Exergy 32 3.6.2 Effect of Reference Environment Composition
3.2.1.1 Standard Chemical Exergy on Chemical Exergy 41
for Components of Air 32 3.7 Case Study: CCPP with Supplemental Firing 43
3.2.2 Standard Chemical Exergy Values for Other 3.7.1 Thermodynamic Modeling, Simulation,
Components 33 and Analysis 43
3.3 Chemical Exergy for Solid Species 34 3.7.1.1 Air Compressor 44
3.4 Chemical Exergy of Gas Mixtures 35 3.7.1.2 CC 45
3.5 Chemical Exergy of Nonenvironmental Substances 3.7.1.3 GT 45
and Fuels 36 3.7.1.4 DB 45
3.5.1 Chemical Exergy of Humid Air 36 3.7.1.5 HRSG 45
3.5.2 Chemical Exergy of Liquid Water and Ice 36 3.7.1.6 ST 46
3.5.3 Chemical Exergy of Gaseous Fuel 36 3.7.2 Exergy Analysis 46
3.5.4 Chemical Exergy of Hydrocarbons 37 3.7.3 Data Use 46
3.6 Effect of Atmospheric Temperature and Pressure and 3.7.4 Results 47
Environment Composition on Chemical Exergy 40 3.8 Closing Remarks 49
Problems 49

ABSTRACT 3.1 INTRODUCTION

In this chapter, we describe chemical exergy and demonstrate its
importance analyzing energy and other systems. Chemical exergy
represents the maximum work extractable from a system at the
pressure and temperature of the reference environment. Alterna-
tively, chemical exergy is the work obtained as a system in
restricted equilibrium with the reference environment is altered to
one in unrestricted (or complete) equilibrium with the. Chemical
exergy is significant when we have chemical reactions (e.g.,
combustion), mixing, and phase change. Chemical exergy is
important in many industrial systems, including electrical gener-
ation stations using combustion, fuel cells where the chemical
energy of a fuel is converted to electricity through a chemical
reaction, biomass gasification devices, distillation columns, and
petrochemical processing plants. To improve understanding,
several examples involving chemical exergy are presented and
subsequently a case study is considered in which a combined cycle
power plant is modeled and assessed comprehensively.
KEYWORDS
Chemical exergy; Chemical exergy definition; Standard chemical
exergy; Reference environment.
Excluding nuclear, magnetic, electrical, and surface tension
effects, exergy has four major parts: physical, chemical,
potential, and kinetic. Kinetic and potential exergy have the
same meaning as the corresponding energy terms. Kinetic
exergy is particularly relevant where speeds are significant,
like in a turbine, whereas potential exergy is especially
relevant for electrical or hydraulic systems. In many practical
cases involving industrial processes, kinetic and potential
exergy terms can be neglected. Physical exergy represents the
maximum amount of work that can be obtained from a system
as its pressure and temperature are changed to the pressure
and temperature of the reference environment.
Chemical exergy represents the maximum work extract-
able from a system at the pressure and temperature of the
reference environment as it changes to a system with the same
composition, as well as pressure and temperature, as the
reference environment. The former condition is often referred
to as the reference-environment state and the latter condition as
the dead state. Alternatively, chemical exergy is the work

Exergy. http://dx.doi.org/10.1016/B978-0-08-097089-9.00003-6
2013 Ibrahim Dincer and Marc A. Rosen. Published by Elsevier Ltd. All rights reserved 31
32 Exergy

obtained as a system in restricted equilibrium with the refer- temperature T can be evaluated relative to the reference
ence environment is altered to one in unrestricted (or complete) environment.
equilibrium with the reference environment. Chemical exergy Note that it is not possible to obtain work by allowing
is important when we have chemical reactions (e.g., combus- substances in the reference environment to interact with
tion), mixing of constituents, and phase change. Since most each other.
energy systems deal with such processes, it is important to A stream of matter also carries chemical exergy,
understand chemical exergy concepts and its calculation. conceptually determined as discussed above for a quantity
Chemical exergy is important in many industrial of a substance.
systems, including electrical generation stations using
combustion, fuel cells where the chemical energy of a fuel 3.2.1 Standard Chemical Exergy
is converted to electricity through a chemical reaction,
biomass gasification devices, distillation columns, and In thermodynamics, the standard molar chemical exergy of
petrochemical processing plants. a component i is defined as consisting of the molar free
In this chapter, we describe chemical exergy and enthalpy Dg0f for the formation of the compound in the
demonstrate its importance in analyzing energy and other standard state from its constituent elements and the stoi-
systems. To improve understanding, several examples chiometric sum of the standard chemical exergy values of
involving chemical exergy are presented and subsequently the elements in their stable states at the temperature T0 and
a case study is considered in which a combined cycle power pressure P0.
plant (CCPP) is modeled and assessed comprehensively.
3.2.1.1 Standard Chemical Exergy
for Components of Air
3.2 CHEMICAL EXERGY DEFINITION
In the natural environment, there are many substances that,
Chemical exergy is equal to the maximum amount of work like oxygen in the atmosphere, cannot react toward a more
that can be obtained when a substance is brought from the stable configuration to produce a new material. They can be
reference-environment state to the dead state by a process considered as part of the reference environment. Trans-
including heat transfer and exchange of substances only formations, including chemical and nuclear reactions,
with the reference environment. The maximum work is cannot convert these components into more stable
attained when the process is reversible. Alternatively, components (Kotas, 1995). So, we cannot extract useful
chemical exergy can also be viewed as the exergy of work from these substances and a specific exergy value of
a substance that is at the reference-environment state. 0 kJ/mol can be assigned to them.
Chemical exergy is also equivalent to the minimum Often, these substances include the normal composition
amount of work necessary to produce a substance at the of air (N2, O2, CO2, H2O, Ar, He, Ne) at T0 298.15 K and
reference-environment state from the constituents in the P0 100 kPa. The partial pressure Pi and molar fraction of
reference environment. Chemical exergy has two main each of these substances in air at a given relative humidity
parts, reactive exergy resulting from the chemical reactions is given in Table 3.1.
necessary to produce species that do not exist as stable
components in the reference environment and concentra-
tion exergy resulting from the difference between the
TABLE 3.1 Partial Pressures and Molar Fractions
chemical concentration of a species in a system and its
of Various Constituents of Air
chemical concentration in the reference environment. The
concentration part is related to the exergy of purifying or Component Pi (kPa) Molar fraction (%)
diluting a substance, such as separating oxygen from air. N2 75.78 75.67
To determine a substances chemical exergy, we need to
O2 20.39 20.34
define a reference environment in terms of its temperature
T0, pressure P0, and chemical composition. In some refer- CO2 0.00335 0.03
ence-environment models, substances present in atmo- H2O 2.2 3.03
sphere, the hydrosphere, and the upper part of the crust of the
earth, at P0 and T0, form the basis of a reference environ- He 0.00048 0.00052
ment. In some models, these substances are allowed to react Ne 0.00177 0.0018
with each other hypothetically and allowed to reach a stable Ar 0.906 0.92
state with a minimum Gibbs energy, at sea level, at rest
without other force fields (Kotas, 1995; Bejan et al., 1996). Kr 0.000097 0.000076
Once a reference environment is defined for an exergy Source: Szargut et al. (1988).
analysis, the exergy of any substance at pressure P and
Chapter | 3 Chemical Exergy 33

With these data, it is possible to determine the their stable condition at T0 298.15 K and P0 101.325 kPa
chemical exergy values of these constituents in the pure are called standard chemical exergies, and these are used
state at P0 and T0. At this condition, air can be treated as in the calculation of chemical of various substances.
an ideal gas at P0, so if the separation into its constituents
Example 3.1: Calculate the molar chemical exergy of
can take place without heat transfer and at T0, with partial
H2O and O2 using the data on partial pressures in Table
pressure, the exergy change of separation can be written
3.1, for a reference state of T0 298.15 K and P0
as follows:
101.325 kPa. The molar universal gas constant is 8.314
DExsep Ex2  Ex1 kJ/kmol K.
Solution: From Table 3.1, the partial pressures for H2O
H2  H0  T0 S2  S0  H1  H0 and O2 are P0;H2 O 2.2 kPa and P0;O2 20.39 kPa.
T0 S1  S0 Using Equation 3.5, the chemical exergies for H2O and
O2 are calculated as follows:
DHsep  T0 DSsep T0 DSsep


(3.1) P0
exch H2 O RT0 ln
P0;H2 O
Here the separation can take place at the same temperature

T2 T1, then: 101:325
8:314  298:15  ln
2:2
DHsep h2  h1 Cp T2  T1 0:
9:49 kJ=mol
The entropy change can be found using the Gibbs

P0
relation as follows: exch O2 RT0 ln
P0;O2


Tds dh  vdP (3.2) 101:325
8:314  298:15  ln
For an ideal gas, we can write the following: 20:39

cp dT v 3:97 kJ=mol
ds  dP (3.3)
T T
So, the change of entropy associated with converting 1 mol
of an ideal gas isothermally from pressure P1 to P2 is given
3.2.2 Standard Chemical Exergy Values
by the following: for Other Components

 To calculate the chemical exergy for other components, we
P2
DS Rln (3.4) may refer to some reactions for which the standard chem-
P1
ical exergies of some components are already given in
With this equation, the standard chemical exergy at P0 for Table 3.2. In this case, we can calculate the chemical
air can be written as follows: exergies for the new components. The following example

 for graphite illustrates how the chemical exergy for
P0
exch RT0 ln
0
(3.5) elements can be determined.
Pi
Example 3.2: Calculate the chemical exergy of
Standard chemical values for the main constituents of air graphite, using the following reaction:
are listed in Table 3.2. Note that exergy values for elements in
Cs O2 g/CO2 g (3.6)
TABLE 3.2 Standard Chemical Exergy Values at P0 Solution: The corresponding change in the standard
and T0 of Various Constituents of Air Gibbs energy is called the standard Gibbs energy of
Component ex 0ch kJ=mol Component ex 0ch kJ=mol formation of CO2, and is defined as follows:
N2 0.72 He 30.37 X X
DG0298:15 f vi moi;298:15  vi moi;298:15 (3.7)
O2 3.97 Ne 27.19 P R
CO2 19.87 Ar 11.69
Here, DG0298:15 denotes the Gibbs energy of formation at
H2O 9.49 Kr 34.36 the reference conditions (Tref 298.15 K, Pref 1 bar),
Sources: Kotas (1995), Bejan et al. (1996). and v is the stoichiometric coefficient, which is positive
for products and negative for reactants. Also, mi Gi,
34 Exergy

which is the standard thermodynamic potential or Gibbs

energy for substance i. Also, subscripts P and R repre- TABLE 3.3 Standard Chemical Values for Selected
sent products and reactants. Similarly, the change of Substances at T0 298.15 K and P0 1 atm
exergy can be written as follows (Bejan et al., 1996): Element ex 0ch kJ=mol Element ex 0ch kJ=mol
X X Ag (s) 70.2 Kr (g) 34.36
ex0ch DG0298:15 f vi moi;298:15  vi moi;298:15
P R Al (s) 888.4 Li (s) 393.0
X X
vi ex0ch;i  vi ex0ch;i Ar (s) 11.69 Mg (s) 633.8
P R
As (s) 494.6 Mn (sa ) 482.3
(3.8)
Au (s) 15.4 Mo (s) 730.3
Then, the exergy of graphite can be calculated as B (s) 628.8 N2 (g) 0.72
follows:
Ba (s) 747.4 Na (s) 336.6

ex0ch;Cs DG0298:15 f 1  ex0ch;CO2 g 1 Bi (s) 274.5 Ne (g) 27.19

 ex0ch;O2 g (3.9) Br2 (l) 101.2 Ni (s) 232.7

C (s, graphite) 410.26 O2 (g) 3.97

Values of the Gibbs energy for various constituents are Ca (s) 712.4 P (s, red) 863.6
given in thermodynamic tables (Cengel et al., 2011), for Cd (sa ) 293.2 Pb (s) 232.8
example, for CO2 the value is 394.35 kJ/mol. So,
Cl2 (g) 123.6 Rb (s) 388.6

ex0ch;Cs 394:35 19:87  3:97 Co (sa ) 265.0 S (s, rhombic) 609.6

410:26 kJ=mol: Cr (s) 544.3 Sb (s) 435.8

Cs (s) 404.4 Se (s, black) 346.5

For substances that are not present in the atmosphere Cu (s) 134.2 Si (s) 854.6
but are in the hydrosphere, we take reference species of
zero exergy level as the most stable state of their exis- D2 (g) 263.8 Sn (s, white) 544.8
tence in seawater. Extensive details about the standard F2 (g) 466.3 Sn (s) 730.2
chemical exergy are given by Szargut et al. (1988). The Fe (sa ) 376.4 Ti (s) 906.9
standard chemical exergy for selected substances are
listed in Table 3.3. H2 (g) 236.1 U (s) 1190.7
The chemical exergy of material substances can also He (g) 30.37 V (s) 721.1
be calculated if the pressure P and the temperature T Hg (l) 115.9 W (s) 827.5
are constant and equal to reference environment
conditions P0 and T0, and the chemical exergy is the I2 (s) 174.7 Xe (g) 40.33
following: K (s) 366.6 Zn (s) 339.2
X Source: Kotas (1995), Bejan et al. (1996).
Exch ni mi  mi0 (3.10)
i

Here, mi and mio are the chemical potentials of substance
i in its state and in the reference environment state,
respectively, and ni is the number of moles. The
chemical potential mi is defined in terms of concentra-
tion c as follows:
mi moi RTlnci
where moi is the standard state chemical potential.
Substitution of Equation 3.11 into Equation 3.10 yields:
X X
Exch ni m0i  m0i0 RT0 ni lnci =ci0 (3.12)
i i
where moio and cio are the chemical potential and
concentrations of component i, respectively, at the
reference conditions. For a single-component system,
Equation 3.12 becomes the following:



c
(3.11) Exch n m0  m00 RT0 ln (3.13)
c0
3.3 CHEMICAL EXERGY FOR SOLID SPECIES
The thermodynamic conditions of chemical species differ on
land relative to conditions in seawater. Mineral substances
Chapter | 3 Chemical Exergy 35

that exist on land can interact with water, oxygen, and other
species to make products. In this regard, the chemical exergy
of some substances from reference species dissolved in
seawater is negative for some common elements on the land
surface such as CaCO3 and MgCO3. So, for elements such as
Mg, Mn, and Co, the assumption that a solid reference
species exists on the land is unavoidable. More details about
the chemical exergy for solid species are given in Szargut
et al. (1988).
3.4 CHEMICAL EXERGY OF GAS MIXTURES
The chemical exergy of a mixture of N gases, in which all
are constituents of the environment, can be obtained similarly.
In this case, we can assume N different chambers (like the one
we already discussed). If each gas has a molar fraction of xk
and enters the chamber at T0 and with a partial pressure xk Po ,
then each gas exits at the same temperature and a partial
pressure xek . Summing for all constituents, the chemical
exergy per mole of the mixture can be calculated as follows:
X
e
x
exch RT0 xk ln k (3.18)
xk

To determine the chemical exergy of a mixture, we consider By writing the logarithmic expression as lnxek  lnxk
the device shown in Figure 3.1, which is a steady-state and using Equation 3.17, this equation can be written as
isothermal chamber in which inlet gas enters at T0 and P0. follows:
The kth gas present in the gas mixture is at T0 and a partial X X
exch xk ex kch RT0 xk lnxk (3.19)
pressure Pek xek P0 , where e denotes the environment and
xek is a mole fraction of gas k in the environment gas phase.
The kth gas entering the chamber at T0 and P0 expands Example 3.3: Calculate the molar chemical exergy of
isothermally and exits to the environment at T0 and xek P0 . a mixture of combustion gases with the following
As discussed earlier, the maximum theoretical work per composition given in Table 3.4. Take T0 298.15 K and
mole of gas k is obtained when there is no irreversibility. By P0 1 bar.
writing an exergy balance the following expression is Solution: We can use Equation 3.15, where k varies
obtained: from 1 to 4. Then:

X
1
w_ CV hi  he  T0 si  se Vi2  Ve2 xk exkch 0:1655  3:97 0:0442  19:87 0:0334
2
  9:49 0:756  0:72
gZi  Ze  T0 S_gen (3.14)
2:39 kJ=mol
In the absence of changes in elevation and velocity, X
xk lnxk 0:165  ln0:165 0:0442  ln0:0442
Equation 3.14 can be simplified as follows:
0:0334  ln0:0334 0:75  ln0:75
w_ CV hi  he  T0 si  se   T0 S_gen (3.15)
0:764
The maximum theoretical work is obtained when the
last term in Equation 3.15 is zero:
Finally,
w_ CV;Max hi  he  T0 si  se  (3.16)
X X
By considering gases to be ideal, the molar chemical exch xk exkch RT0 xk lnxk


exergy is obtained using Equation 3.4 as follows: 8:314

e  2:39  298:15  0:764
x P0 1000
ex kch RT0 ln k RT0 lnxek (3.17)
Po 0:49 kJ=mol

TABLE 3.4 Mole Fraction of Combustion Gases

Combustion Mole Standard molar chemical

product fraction (%) exergy (kJ/mol)
Gas k at Gas k at
O2 16.55 3.97
0 0
0
CO2 4.42 19.87
H2O 3.34 9.49
N2 75.6 0.72
0

FIGURE 3.1 Isothermal chamber.

36 Exergy

3.5 CHEMICAL EXERGY OF

NONENVIRONMENTAL SUBSTANCES
AND FUELS
3.5.1 Chemical Exergy of Humid Air
The state of the local atmosphere is determined by its
intensive parameters: T0, P0, and its composition. For
humid air, the gas composition for all species other than
FIGURE 3.2 Chamber to calculate work and chemical exergy of
vapor can be considered fixed. So, the composition varia- hydrocarbon.
tion is linked to the moisture content. To calculate the
molar fraction of water vapor, we use the following: Here, F denotes fuel, and n_ F is the molar flow rate of
Pgas;0 fuel. Note that in this equation the effects of both kinetic
xeH2 o 4 (3.20) and potential energy changes are treated as negligible.
P0
If heat transfer occurs at temperature T0, the entropy
Here 4 is relative humidity and Pgas,0 is the saturation balance for a control volume around the chamber follows:
pressure at T0. In the case when molar fraction of dry air is

assumed to be constant, the local atmospheric molar 1 Q_ =n_ F 1 s_gen
sF x y sO2 CV xsCO2  ysH2 O
fraction of gases other than water is expressed as 4 T0 2 n_ F
xei 1  xeH2 O xdry
i , in which molar fraction of compo- (3.24)
nent i corresponds to the atmospheric partial pressure of the
species. By eliminating the heat transfer rate from Equation 3.23
using Equation 3.24, an expression can be obtained for
work per mole of fuel as follows:
3.5.2 Chemical Exergy of Liquid Water 
 
and Ice W_ CV 1 1
hF x y hO2  xhCO2  yhH2 O
n_ F 4 2
The molar chemical exergy of liquid water is expressed as 
 
1 1
follows (Szargut et al., 1988):  T0 sF x y sO2  xsCO2  ysH2 O
  4 2
exwch v P0  Pgas;0  RT0 ln4 (3.21)
s_gen
 T0
Here, y is the molar fraction of compressed water, Pgas,0 n_ F
is the saturation pressure at T0, and 4 is relative humidity. (3.25)
This equation is valid for solid water (ice) as well (Szargut
A corresponding exergy rate balance can be written as
et al., 1988).
follows:
X X
3.5.3 Chemical Exergy of Gaseous Fuel _ Q
Ex m_ i exi _ w Ex
m_ e exe Ex _ D (3.26)
i e
To calculate the chemical exergy of a substance, which is
not present in the reference environment, we can consider Since this reaction is considered to be ideal, the exergy
an ideal reaction of that substance with other substances destruction term in Equation 3.26 is equal to zero. Other
from the reference environment, such as fuels. terms in this equation are explained as follows:



To illustrate the determination of the chemical exergy
_ T0 Q_ CV _ W_ CV
for a pure hydrocarbon fuel with CxHy at T0 and P0, we ExQ 1  ; ExW ;
Tj n_ F n_ F
consider Figure 3.2, where fuel is reacted with oxygen to

form CO2 and liquid water according to the following: 1 1 ch
exi exch
F x y exO2 and exe xexO2 yexH2 O :
ch ch

 4 2
1 1
Cx Hy x y O2 /xCO2 yH2 O (3.22)
4 2 By substituting these terms in Equation 3.20, we obtain
A steady-state energy rate balance for the chamber in the following:



Figure 3.2 can be written as follows: T0 Q_ CV 1
1 exF x y exch
ch

 Tj n_ F 4 O2
W_ CV Q_ CV 1 1

hF x y hO2  xhCO2  yhH2 O W_ CV
n_ F n_ F 4 2 xexch
1 ch
O2 yexH2 O 0 (3.27)
(3.23) 2 n_ F
Chapter | 3 Chemical Exergy 37


T0 Q_ CV 3.5.4 Chemical Exergy of Hydrocarbons
The term 1  represents the rate of exergy
Tj n_ F Consider a system in an environment containing a quantity
transfer associated with heat transfer rate Q_ CV occurring at of hydrocarbon fuel with chemical formula, CxHy. To
the location on the boundary where the temperature is Tj. determine how work may be obtained through a reaction of
Since heat transfer occurs at the reference-environment the fuel, we refer to a cell operating at steady-state condi-
temperature, that is, Tj T0, the first term on the left side of tions, as shown in Figure 3.2. The fuel (CxHy) enters the
Equation 3.27 is zero. So: system at T0 and P0. Assuming the reference environment


 consists of an ideal gas mixture, then oxygen can be viewed
W_ CV 1 ch 1 as entering the system at its condition in the environment,
F
exch xexch yex  x y exch
n_ F O2
2 H2 O 4 O2
which is T0 and partial pressure of xO2 P0 , where xO2 is the
(3.28) molar fraction of oxygen in the reference environment. In
the cell, fuel and oxygen react to produce carbon dioxide
The first term on the right side of Equation 3.28 can be and water vapor, which are the products of the cell, at
written as a function of the higher heating value of the fuel partial pressures xCO2 P0 and xH2 O P0 . According to Equa-
and the entropy difference between reactants and products tion 3.25, the specific enthalpy and entropy of the fuel can
in the combustion reaction. Then, this equation becomes be calculated at T0 and P0. The values for the specific
the following (Bejan et al., 1996): enthalpies in the first bracketed term on the right side of this
equation are calculated by knowing the temperature T0;
however, the specific entropies in the second bracketed
F HHVT0 ; P0
exch term are evaluated via the temperature, the pressure, and

  the composition of the reference environment. The
1 y
 T0 sF x y sO2  xsCO2  sH2 O maximum theoretical value for the work based on Equation
4 2 T0 ;P0 3.25 is obtained when there is no irreversibility. In this case,

 the last term in Equation 3.25 is zero and this maximum
1 ch 1
xexch
O2 yex  x y exch (3.29) work is equal to chemical exergy, as follows:
2 H2 O 4 O2

 
1 1
Also, using the definition of specific Gibbs function, exch hF x y hO2  xhCO2  yhH2 O
4 2
g h  T s, Equation 3.29 can be alternatively expressed 
 
1 1
as follows:  T0 sF x y sO2  xsCO2  ysH2 O
4 2

 
1 y (3.32)
exch
F gF x y gO2  xgCO2  gH2 O
4 2 T0 ;P0 Knowing that si T0 ; xi P0 si T0 ; P0  Rlnxi (Bejan


1 ch 1 et al., 1996), Equation 3.32 can be modified to the
xexch
O2 yexH2 O  x y exO2
ch
following:
2 4

 
(3.30) 1 1
exch hF x y hO2  xhCO2  yhH2 O
4 2 T0 ;P0
To assist in determining the chemical exergy of fuels, 
 
1 1
Szargut et al. (1988) provided values of the exergy to  T0 sF x y sO2  xsCO2  ysH2 O
energy ratio, F exf =LHV. For most hydrocarbons, this 4 2 T0 ;P0
" #
ratio is near unity. For common gaseous fuels, for instance, 1
x4y
xO2
the ratio of chemical exergy to lower heat value for RT0 ln y

methane and hydrogen are FCH1 1:06, and xCO2 x xH2 O 4

FH2 0:985. Szargut et al. (1988) provided the correla- (3.33)
tion for liquid fuels (CaHbNgOd), based on their atomic
This equation can also be evaluated in terms of the
compositions as follows:
Gibbs functions as follows:
b d 
 
F 1:0401 0:1728 0:0432 1 y
a a exch gF x y gO2  xgCO2  gH2 O

 4 2 T0 ;P0
g b " #
0:2169 1  2:062 (3.31) xO2 x14y
a a RT0 ln y
b b g xCO2 x xH2 O 4
where , , and are the atomic ratios of the fuel.
a a a (3.34)
38 Exergy

CH4 To find the molar fraction of combustion gases,

T2
carbon, hydrogen, oxygen, and nitrogen balances are
written as follows:

Air Combustion Combustion 0:7748 0:2059  2l

Chamber Gases xN2  ; xO2 
T1 T3 l1 l1
FIGURE 3.3 CC used in GT cycle.
0:0003 l 0:019 2l
Example 3.4: The combustion chamber (CC) is a major xCO2 ; xH2 O
l1 l1
component of both gas turbine (GT) and combined cycle
plants. A CC for a GT engine is shown in Figure 3.3.
Compressed air enters at point 1, methane (CH4) fuel is The molar breakdown of the combustion gases is
injected into the CC at point 2, and the fuel mass flow known once l is determined. An energy rate
rate is 1.5 kg/s. Combustion gases exit at point 3. In this balance is used to determine the fuel-air ratio as
example, air enters the CC at T1 550 K and P1 10 bar follows:
and the combustion gases exit at T3 1400 K. The molar
composition of air is 0.7748 for N2, 0.2059 for O2,
Q_ CV  W_ CV n_ F hF n_ a ha  n_ p hp 0
0.0003 for CO2, and 0.019 for H2O. The following
assumptions are made:
l The CC operates at steady state.
Since the heat loss from the CC is 2% of LHV of the
l The air and combustion gases are both treated as
fuel,
ideal gas mixtures.
l Combustion is complete.
Q_ CV  0:02n_ F LHV  n_ a 0:02l  LHV
l Potential and kinetic effects are negligible.

l Heat loss from the CC is 2% of the lower heating

value (LHV) of the fuel. Combining the above two equations yields the
1. Determine the fuel-to-air ratio, and the molar fractions following:
of the combustion gases.
2. Find the specific physical and chemical exergy values at 0:02l LHV ha l hF  1 lhP 0
point 3.
3. For a reference state of T0 298.15 K and P0
Employing ideal gas mixture principles to calculate
101.325 kPa, determine the exergy destruction rate and
the enthalpies of the air and combustion gases, where
exergy efficiency of the CC.
T1 550 K and T3 1400 K, we obtain the
4. Compare the results with information in the literature.
following:
Solution:
Part 1:
To solve this problem, we first define the molar fuel- ha 0:7748hN2 0:2059hO2 0:0003hCO2
air ratio l as the following:
n_ F 0:019hH2 O at T1
l
n_ a

1
So: hP 0:7748hN2 0:2059  2lhO2
l1
n_ P n_ a n_ F
l1
n_ a n_ a
0:0003 lhCO2 0:019 lhH2 O at T3
On a per mole of air basis, the combustion equation
occurring in the CC can be written as follows: Then, solving the energy rate balance for l yields the
following:
lCH4 0:7748 N2 0:2059 O2 0:0003 CO2
0:019 H2 O / l 1xN2 N2 xO2 O2 0:7748DhN2 0:2059DhO2 0:0003DhCO2 0:019DhH2 O
l
xCO2 CO2 xH2 O H2 O hF  0:02LHV  2hO2 hCO2 2hH2 O T4
Chapter | 3 Chemical Exergy 39

Using enthalpy values from thermodynamic tables dew point temperature can result in condensation. For
(Cengel et al., 2011) and considering the following: example, if the combustion gas mixture were cooled
to 25 C at a fixed pressure of 1 atm, some conden-
hF 74; 872 kJ=kmol; sation would occur. In this case we can model results
at 25 C as a gas phase containing saturated water
LHV 802; 361 kJ=kmol vapor in equilibrium with a liquid water phase. To find
the dew point temperature, we first calculate the
we find l 0:0393. Using this value and the partial pressure of water vapor. According to Part 1,
combustion gas molar fractions determined earlier, the molar fraction of H2O in the combustion gases is
the following molar breakdown of the combustion 0.0939, so the partial pressure of water vapor is
products is obtained: Pv xv P0 0:09391:013 bar 0:0951 bar.
The corresponding saturation temperature at this
pressure is 44.81 C; the reference environment
Component N2 CO2 H2O O2
temperature is therefore below the dew point, which
Molar breakdown (%) 74.55 3.81 9.39 12.24 leads to the formation of liquid water. On the basis of
1 kmol of combustion products, the gas phase at
25 C consists of 0.9061 kmol of dry products (0.7455
Part 2:
N2, 0.3810 CO2, 0.1224 O2) plus nv kmol of water
To calculate the specific physical exergy at point 3,
vapor. The partial pressure of water vapor is equal to
the specific physical exergy expression described
the saturation pressure at 25 C, which is 0.0317 bar.
earlier is employed as follows:
The amount of water vapor is calculated as
exph;3 h3  h0  T0 s3  s0 Pv xv P0 nv =0:9061 nv  P0 , where nv is


 the amount of water vapor. Hence, 0:0317 bar
T3 P3
Cp T3  T0  T0 Cp ln  Rln nv  1:013 bar=0:9061 nv , which yields nv
T0 P0
0:02927 kmol. Thus, the molar fractional composi-
tion of the combustion products at 25 C and 1 atm is
Since the pressure drop through the CC is treated as
0.7455 N2, 0.3810 CO2, 0.1224 O2, 0.02927 H2O (g),
negligible P3 P1 10 bar. For the combustion
and 0.06583 H2O (l). At point 3 in the present
gases, we consider a fixed specific heat at constant
analysis, 0.06583 kmol liquid water is present on the
pressure as Cp 1.14 kJ/kg K. Substituting these
basis of 1 kmol mixture, following the method out-
values into specific physical exergy expression
lined by Bejan et al. (1996). Therefore, the exact
yields exph;3 933:1 kJ=kg.
specific chemical exergy at point 3 after modification
To determine the specific chemical exergy at point 3, is as follows:
Equation 3.15 is used as follows:
900
exch;3 1  0:06583  22:95 0:06583 
X X 18
exch;3 xk exkch RT0 xk lnxk
24:32 kJ=kg
0:1224  3970 0:0381  19870
0:0939  9490 0:745  720 Here, the first term is the percentage of dry
8:314  298:15  0:1224ln0:1224 combustion gases multiplied by the specific chem-
ical exergy obtained from Part 2, and the second term
0:0381ln0:0381 0:0939ln0:0939 is the product of the molar fraction of liquid water
0:745ln0:745 due to the condensation and specific chemical exergy
kJ kJ of liquid water.
632:1 22:95
kmol kg Finally, the specific exergy at point 3 can be deter-
mined as follows:
When a mixture including gaseous combustion kJ
products containing water vapor is cooled at ex3 exch;3 exph;3 24:32 933:1 957:42
kg
a constant pressure, the dew point temperature, which
is the saturation temperature corresponding with the
partial pressure of water vapor, is the temperature at Part 3:
which the formation of liquid water begins. Thus, To allow the exergy destruction rate of the CC to be
cooling such a mixture at constant pressure below the calculated, all mass flow rates are determined. With
40 Exergy

the fuel-air ratio of 0.0393 found in Part 1 and the Here, ex1 and ex2 are the specific exergy at points 1
given mass flow rate of fuel (CH4) of 1.5 kg/s, we can and 2, respectively, and exf is the fuel exergy.
determine the mass flow rate of air into the CC as Recalling that the heat loss from the CC is 2% of the
follows: LHV of the fuel, this equation can be solved for the
exergy destruction rate as follows:
1:5


n_ F kg 298:15
l 16 0:0393/m_ a 71:42 _
ExD 0:02  m_ f  LHV 1 
n_ a m_ a s 1400
29 71:42  281:7 1:5  1:06  50;147:5
 1:5 71:42  957:42 31:22 MW
To determine the chemical exergy of the methane fuel
injected into the CC, Equation 3.24 is used as follows:
The exergy efficiency j for CC is defined as
exf F  LHV follows:

_ 3
Ex

_ _ _ Q
Ex1 Exf Ex
1:5 71:42  957:42

 69%
298:15
71:42  281:7 1:5  1:06  50147:5 0:02  m_ f  LHV 1 
1400

where FCH4 1:06 and LHV CH4 802;361 kJ=kmol Part 4:

50;147:5 kJ=kg. Many studies have been reported in the literature
To calculate the exergy destruction rate in the CC, all with which the present results can be compared.
exergy flow rates are needed. Since, the specific Here, the present results regarding the molar frac-
physical and specific chemical exergy values at point tions of the combustion gases are compared with
3 are calculated in Part 2, we now need to calculate those of Ameri et al. (2008). In their work T1 594
specific exergy at point 1: K and T3 1244 K. Although these temperatures
differ slightly from the ones used here, the present
results show a good agreement with those of Ameri
exph;1 h1  h0  T0 s1  s0


 et al. (2008), as shown in the following tabulation:
T1 P1
Cp T2  T0  T0 Cp ln  Rln
T0 P0 Component N2 CO2 H2O O2
kJ
281:7 Molar fraction (%) 74.55 3.81 9.39 12.24
kg (present example)
Molar fraction (%) 75.6 4.42 3.34 16.55
To determine the exergy destruction rate, we can (Ameri et al., 2008)
employ a general exergy balance as follows:

X X 3.6 EFFECT OF ATMOSPHERIC

_ Q
Ex m_ i exi _ w Ex
m_ e exe Ex _ D
TEMPERATURE AND PRESSURE AND
i e
ENVIRONMENT COMPOSITION ON
which can be expressed for the CC as follows: CHEMICAL EXERGY
The state of local atmospheric condition can be defined by

 the temperature T0 and pressure P0 and its composition
T0
Q_ CV 1  m_ 1 ex1 m_ f exf m_ f m_ 1 ex3 (Ertesvag, 2007). The concentration of gases other than
T3
water vapor can be considered constant. Therefore,
Ex _ D
composition changes are attributable to the moisture
Chapter | 3 Chemical Exergy
content. When the mole fraction of dry air (i.e., air without
H2O) is considered constant, the local atmospheric fractions
of gases, except H2O, are expressed as xei 1  xeH2 O xdryi
Here xdry e
i is the dry mole fraction of substance i and xH2 O is as
previously defined in Equation 3.6. The dry air model
fractions are 0.78084 for N2, 0.20941 for O2, 0.000375 for
CO2, and 0.00934 for Ar (Szargut et al., 1988). According to
Szargut et al. (1988), the reference relative humidity is 0.7%,
which means that at 25 C and 1 atm the molar fraction of
H2O is 0.02189. To compare the changes in chemical exergy,
a relative deviation is defined as RD (exch,i /exch,i ref)  1.
3.6.1 Chemical Exergy Variation with
Temperature and Moisture Content
The variation of chemical exergy with ambient temperature
is shown in Figure 3.4. Here, we consider only the atmo-
spheric gases N2, O2, CO2, and water vapor. It is observed
that, due to the variation of saturation pressure of water,
water vapor plays a significant role in the variation of
chemical exergy. As shown in this figure, other atmospheric
gases have the opposite tendency compared to water vapor.
This trend is mainly due to the proportionality of chemical
exergy with temperature, as given in Equation 3.5. As
another example, the variation of chemical exergy for N2
with both ambient temperature and relative humidity is
shown in Figure 3.5. It is seen that an increase in ambient
temperature leads to an increase in chemical exergy of N2
and also at constant ambient temperature an increase in
relative humidity results in an increase in chemical exergy
of N2. The reason for this increase is that as the maximum
dilution with water vapor rises with temperature, the vari-
ation with relative humidity increases. The effect of vari-
ation of chemical exergy with relative humidity of some
atmospheric gases is shown in Figure 3.6. It is concluded
80
Chemical exergy relative deviation (%)
60
40
20
-20
-40
-30 -20 -10
Ambient temperature (C)
41
that relative humidity has a major effect on chemical exergy
of water vapor and N2.
3.6.2 Effect of Reference Environment
Composition on Chemical Exergy
The reference environment is in stable equilibrium, with all
parts at rest relative to one another. No chemical reactions
can occur between the environmental components. The
reference environment acts as an infinite system, and is
a sink and source for heat and materials. The exergy of the
reference environment is zero, and the exergy of a stream or
system is zero when it is in equilibrium with the reference
environment. Chemical exergy is dependent on the selec-
tion of a reference environment model, so chemical exergy
values vary with the definition of the reference environ-
ment. The terms reference environment and natural envi-
ronment are explained and differentiated in Section 2.8.1.
Various reference environment models are explained in
Chapter 2. As already explained, the atmosphere can serve
as an appropriate reference state for only about 10 chemical
species. For other chemical species, convenient reference
species can be species that are most commonly found on
the surface of the earth (Szargut et al., 1988). However,
defining the chemical composition of the earth is some-
times difficult and can make consistent evaluations of
exergy challenging.
Szargut et al. (1988) proposed that ions or compounds
dissolved in seawater be used as the reference species for
some elements. Hence, ionic reference species are adopted
when these elements appear in seawater in the form of
monocharged or bicharged ions. The average values of
mass fraction of elements in seawater from different sour-
ces are listed by Szargut et al. (1988). Various different
models for the reference environment have been proposed,
FIGURE 3.4 Variation of chemical exergy with ambient
temperature for selected atmospheric gases at P0 1 atm and
H2 O N2
70% relative humidity. The relative deviation in percentage is
O2 CO
O2 relative to the values at reference conditions of 25 C, 1 atm,
and 70% relative humidity.
0 10 20 30 40
42 Exergy

FIGURE 3.5 Variation of chemical exergy for nitrogen, N2,

at an ambient pressure of 1 atm, with ambient temperature
and relative humidity.

some of which are in thermodynamic equilibrium, but with 1. Szargut et al. (1988), in which the molar fraction of
compositions and parameters that differ from those in the the reference species is 0.472.
natural environment. Others consider species that are found 2. Rivero and Garfias (2006), in which the molar
in abundance in the natural environment, which are not fraction of the reference species is 0.407.
generally in thermodynamic equilibrium as the reference. In both cases, the reference species is SiO2(s), and the
To simplify, Szargut et al. (1988) suggested that the reference-environment temperature T0 298.15 K and
chemical exergy obtained in the standard state at normal the reference-environment pressure P0 1 atm. The
temperature and pressure should be considered as standard molar universal gas constant is 8.314 kJ/kmol K.
chemical exergy with respect to the conventional mean Solution:
concentrations of the reference species in the environment. Part 1:
By knowing the standard chemical exergy values of In Szarguts reference environment model, xi
elements, the standard chemical exergy values for any 0.472 for SiO2(s), so the standard specific chemical
chemical compound are calculated using Equation 3.7. exergy of this species is calculated using Equation
To illustrate the effect of reference species on chemical 3.17 as follows:
exergy, the following example is provided.
ex0ch;SiO2 RT0 lnxi
Example 3.5: Calculate and compare the specific
chemical exergy of silicon using two different 8:314  298:15  ln0:472
approaches: 1:861 kJ=mol

FIGURE 3.6 Variation of chemical exergy with ambient rela- 10

Chemical exergy relative deviation (%)

tive humidity for selected atmospheric gases at an ambient

H2O
pressure 1 atm and a temperature 25 C. O2
N2 CO2

-10
0.2 0.4 0.6 0.8 1
Relative humidity,
Chapter | 3 Chemical Exergy
To calculate the specific chemical exergy of Si(s), the
exergy balance of the reaction of formation of the
reference species, SiO2(s), is required. The reaction
is as follows:
Sis O2;g /SiO2;s greenhouse gas emissions, and operational flexibility. In
Using Equation 3.7 and knowing that DG0SiO2
856:67 kJ=mol and ex0ch;O2 3:97 kJ=mol from
Table 3.2:
ex0ch;Si ex0ch;SiO2  DG0SiO2  ex0ch;O2
1:861 856:67  3:97 854:56 kJ=mol
Part 2:
In the reference environment model of Rivero and
Garfias (2006), xi 0.407 for SiO2(s), so the stan-
dard specific chemical exergy of this species is
calculated using Equation 3.7 as follows:
ex0ch;SiO2 RT0 lnxi
8:314  298:15  ln0:407
2:228 kJ=mol
Using the exergy balance of the reaction of SiO2(s)
given in Part 1 and DG0SiO2 , the standard specific
chemical exergy for Si(s) is calculated as follows:
ex0ch;Si ex0ch;SiO2  DG0SiO2  ex0ch;O2
2:228 856:67  3:97 854:96 kJ=mol
A comparison reveals that the difference in the
reference-environment molar fraction leads to a 0.4
kJ/mol variation in specific chemical exergy.
Further details about the effect of reference envi-
ronment variations on chemical exergy are provided
by Rivero and Garfias (2006). They observe that
the reference species of elements bismuth, molyb-
denum, and wolframium change from the litho-
sphere to the hydrosphere, whereas for magnesium,
cobalt, and phosphorous, the reference species from
the earths crust are selected instead of the hydro-
sphere. After 1989, the reference species in the
earths crust were selected instead of the species in
the seawater for calcium, barium, gold, and fluorine
(Rivero and Garfias, 2006). Recently, a reference
species of the lithosphere was preferred for arsenic
instead of a reference species of the hydrosphere.
43
3.7 CASE STUDY: CCPP WITH
SUPPLEMENTAL FIRING
CCPPs have recently received considerable attention due
to their relatively high efficiencies, low pollutant and
this case study, we consider a common CCPP, the gas-
steam combined cycle (see Figure 3.7), which is comprised
of a GT cycle (topping cycle) and a steam turbine (ST)
cycle (bottoming cycle) coupled through a heat recovery
steam generator (HRSG). The cycle includes supplemental
firing. The case study illustrates how chemical exergy is
calculated and describes its relation to cycle design
parameters such as cycle exergy efficiency and exergy
destruction rate.
3.7.1 Thermodynamic Modeling, Simulation,
and Analysis
The modeling and analysis of the CCPP with supple-
mental firing are described in this section. A simulation
program developed with MATLAB software is utilized to
assist in analysis and optimization, for example, for
determining the optimum physical and thermal design
parameters of the system. The steam and gas temperature
profiles in the CCPP, and the input and output enthalpy
and exergy values for each flow in the plant, are deter-
mined through a multi-objective optimization of the plant.
Energy balances and governing equation for various CCPP
components are described in the following subsections.
These equations are subsequently used to determine the
state properties (e.g., temperature, enthalpy) of each flow
in the plant.
The CCPP is illustrated in Figure 3.4, which also
includes descriptions of the flows. Air at ambient conditions
enters the air compressor at point 1 and, after compression
(point 2), is supplied to the CC. Fuel (CH4) is injected into
the CC and hot combustion gases exit (point 3) and pass
through the GT to produce electricity. The hot gas expands
in the GT to point 4. A duct burner (DB) is used to increase
the temperature of flue gas exiting the GT. The hot flue gas
leaving the DB (point 5) is utilized in an HRSG to generate
superheated vapor (point 8). Superheated vapor enters the
ST and produces electricity (point 13).
Several simplifying assumptions are made in the
analysis, following earlier approaches (Ahmadi et al.,
2011a,b):
l All processes are assumed steady-state and steady-flow.
l Air and combustion products are treated as ideal-gas
mixtures.
l The fuel injected into the CC is natural gas.
l All components are considered adiabatic except the CC,
for which heat losses occur.
44 Exergy

16

Flow Description
1 Compressor inlet air
2 Compressor outlet air
3 Combustion gases exiting combustion chamber
4 Gas turbine outlet gases
5 Combustion gases exiting duct burner
6 HRSG outlet gases
7 Water entering HRSG
8 Superheated steam entering steam turbine
9 Outlet steam from steam turbine
10 Saturated liquid entering feed water pump
11 Cooling water entering condenser
12 Cooling water exiting condenser
13 Steam turbine gross output power
14 Gas turbine gross output power
15 Compressor work
16 Pump work
a Economized outlet
b Evaporator outlet
c Hot gases leaving the superheater
d Hot gases leaving the evaporator
FIGURE 3.7 Schematic of a GT CCPP with supplemental firing (modified from Ahmadi et al., 2011a). m_ f ;CC and m_ f ;DB denote the mass flow rates
injected into the CC and DB. Cond denotes condenser. Other device symbols are defined in the text.

3.7.1.1 Air Compressor

l The reference-environment conditions are P0 1.01 bar,
T0 293.15 K, and a molar composition of air of 0.7748 Air at ambient pressure (1 bar) and temperature T1 enters
for N2, 0.2059 for O2, 0.0003 for CO2, and 0.019 the compressor. The compressor outlet temperature is
for H2O. a function of compressor isentropic efficiency hAC,
Chapter | 3 Chemical Exergy 45

compressor pressure ratio rAC and specific heat ratio for air 3.7.1.3 GT
ga as follows:


 The GT outlet temperature T4 can be written as a function
1 ga 1 of the GT isentropic efficiency hGT, inlet temperature T3,
T2 T1  1 rAC g a 1 (3.35)
hAC pressure ratio (P3/P4), and the specific heat ratio for the
combustion gases gg as follows:
The compressor work rate is a function of air mass flow


1gg 
rate m_ a , the air specific heat at constant pressure Cpa, and P3 gg

the temperature difference across the compressor, and can T4  T3 1  hGT 1 (3.41)
P4
be expressed as follows:
The GT output power (gross) can be expressed as follows:
W_ AC m_ a Cpa T2  T1 (3.36)
W_ GT m_ g Cpg T3  T4 (3.42)
Here, Cpa is treated as a function of temperature as
follows (Ahmadi et al., 2011a): Here, m_ g is the gas mass flow rate through the GT which, by
conservation of mass, can be determined as follows:




3:83T 9:45T 2 5:49T 3 m_ g m_ f m_ a (3.43)
Cpa T 1:048  
104 107 1010

 and Cpg is taken to be a function of temperature as follows
7:92T 4 (Ahmadi et al., 2011a):

1014


6:997T 2:712T 2
(3.37) Cpg T 0:991
105 107


1:2244T 3
 (3.44)
3.7.1.2 CC 1010
The outlet gas properties of the CC are a function of air The GT net output power can be expressed as follows:
mass flow rate, the fuel LHV, and CC efficiency hcc, and
related as follows: W_ Net W_ GT  W_ AC (3.45)

m_ a h2 m_ f LHV m_ g h3 1  hcc m_ f LHV (3.38)

Here, h2 and h3 denote, respectively, the specific 3.7.1.4 DB
enthalpies for the compressed air (point 2) and the
Additional fuel (CH4) is burned in the DB, a supplemental
combustion gas (point 3), and m_ f and m_ g denote, respec-
firing unit, to increase the temperature of the exhaust gas
tively, the mass flow rates of the fuel and the combustion
that passes through the HRSG. An energy balance for the
gas.
DB can be written as follows:
The CC outlet pressure is related to the pressure drop
across the CC 6Pcc as follows: m_ 4 h4 m_ f ;DB LHV m_ 5 h5 1  hDB m_ f ;DB LHV
(3.46)
P2
1  DPCC (3.39) where LHV is the LHV of the methane fuel and hDB is the
P2
DB combustion efficiency, which is taken to be 94% based
Following Example 3.4 (Part 1), if complete combus- on values reported elsewhere (Ahmadi et al., 2011a).
tion is assumed to occur in the CC, we can write the
combustion equation with its species coefficients as
follows: 3.7.1.5 HRSG
lCH4 0:7748 N2 0:2059 O2 0:0003 CO2 0:019 H2 O To calculate the temperature of each part of the HRSG, it is
divided into three different sections: economizer, evapo-
/l 1xN2 N2 xO2 O2 xCO2 CO2 xH2 O H2 O
rator, and superheater, denoted by labels a, b, c, and d in
Figure 3.7. The purpose of dividing the HRSG into three
Here:
subsections is to calculate the HRSG outlet temperature and
0:7748 0:2059  2l ST inlet temperature using the HRSG pinch-point temper-
x N2 ; xO2 ;
l1 l1 atures. The pinch-point temperature is the temperature
(3.40) difference between the hot gas leaving the evaporator and
0:0003 l 0:019 2l
xCO2 ; xH2 O the evaporator saturation temperature. So, by applying an
l1 l1
energy balance for gas and water in each part of the HRSG,
46 Exergy

the gas temperature and water properties are calculated in The causes of exergy destruction in the units have been
each part of the HRSG by solving the following: investigated in the past. For instance, the main sources of
exergy destruction in the CC are combustion (chemical
m_ w ha  h7 m_ g Cpg Td  T6 (3.47)
reaction), heat transfer across large temperature differ-
m_ w hb  ha m_ g Cpg Tc  Td (3.48) ences, and thermal losses in the flow paths, while exergy
destruction in the primary heat exchanger (the HRSG) is
m_ w h8  hb m_ g Cpg T5  Tc (3.49)
mainly due to the large temperature differences between
where Cpg is determined with Equation 3.44. the hot and cold fluids.

3.7.1.6 ST 3.7.3 Data Use

For the ST in Figure 3.4, the output power is expressible as The performance of the CCPP with supplemental firing is
follows: described considering realistic conditions for each compo-
W_ ST m_ w h8  h9 (3.50) nent, based on typical industry values. We consider a fixed net
output power of the GT cycle at 100 MW. The compressor
Also, the ST isentropic efficiency is defined as follows: inlet air is taken to be at 1 atm and 298 K. Heat losses from the
W_ ST;act m_ w h8  h9;act CC are assumed to be 2% of the energy input to the CC based
hST (3.51) on the LHV of the fuel (Ahmadi et al., 2011a). Isentropic
W_ ST;is m_ w h8  h9;is
efficiencies are taken to be constant, at 83% for the
Here, h9,act and h9,is are the actual and isentropic compressors and 90% for both the gas and STs. The exhaust
enthalpies at point 9, respectively. gas temperature at the HRSG exit is maintained above the
condensation temperature of combustion products. The steam
conditions at the ST inlet are set at 8 MPa and 400 C, and the
3.7.2 Exergy Analysis
condenser pressure in the steam cycle is 0.10 bar.
Exergy analysis is applied to determine the exergy Ranges are considered for some system parameters, to
destruction and exergy efficiency for each component of the allow sensitivity studies. The gas turbine inlet temperature
CCPP. Expressions for these exergy parameters are given in (GTIT) is varied between 1150 and 1500 K, and the oper-
Table 3.5, consistent with other exergy analyses of similar ation range for the compressor pressure ratio is constrained
systems (Ameri et al., 2008; Ahmadi et al., 2011a,b). between 12 and 25. Variations in other operating conditions

TABLE 3.5 Expressions for Exergy Destruction Rate and Exergy Efficiency for CCPP Component

Plant component Exergy destruction rate Exergy efficiency

_ 2  Ex
Ex _ 1
Air Compressor _ D;AC Ex
Ex _ 1  Ex
_ 2 W_ AC j AC
W_ AC
_ 3
Ex
Combustion chamber _ D;CC Ex
Ex _ 2 Ex
_ f ;CC  Ex
_ 3 j CC
_ 2 Ex
Ex _ f ;CC

_ D;GT Ex
_ 3  Ex
_ 4  W_ GT W_ GT
Gas turbine Ex j GT
_ 3  Ex
Ex _ 4

_ 5
Ex
Duct burner _ D;DB Ex
Ex _ 4  Ex
_ 5 Ex
_ f ;DB jDB
_ 4 Ex
Ex _ f ;DB

_ D;Cond
Ex
Condenser _ D;Cond Ex
Ex _ 11 Ex
_ 10  Ex
_ 9  Ex
_ 12 j Cond 1 
_ 11 Ex
Ex _ 10

_ 8  Ex
Ex _ 7
Heat recovery steam generator _ D;HRSG Ex
Ex _ 5 Ex
_ 7  Ex
_ 6  Ex
_ 8 j HRSG
_ _ 6
Ex5  Ex

_ D;ST Ex
_ 8  Ex
_ 9  W_ ST W_ ST
Steam turbine Ex j ST
_
Exi;ST  Ex_ o;ST

_ 7  Ex
Ex _ 10
Pump _ D;P Ex
Ex _ 7  Ex
_ 10 W_ P jP
_
WP
Chapter | 3 Chemical Exergy 47

are also investigated, including compressor pressure ratio
and degree of supplemental firing.
3.7.4 Results
Exergy destructions for the components in the CCPP are
shown in Figure 3.8. The exergy analysis results demon-
strate that, for the operating conditions considered, the CC
incurs the most significant exergy destruction in the CCPP.
This result is attributable to the significant irreversibilities
associated with chemical reaction and heat transfer across
the large temperature differences between the burner gases
and the working fluid. The exergy destruction with
combustion is linked to the nature of the process considered
here and, to reduce this exergy destruction significantly,
efficiency improvements can be sought and alternative
systems need to be considered.
Since chemical reaction is one of the main reasons for
the high exergy destruction rate in the CC, it is important to
understand how both physical and chemical exergy at the
exit of the CC (point 3 in Figure 3.7) vary with operating
and design parameters. According to Figure 3.8, the exergy
destruction rate for the CC is strongly dependent on the
exergy at point 3, and increasing this exergy leads to
a decrease in the total exergy destruction rate of the CC for
a constant compressor pressure ratio.
The effect of GTIT on both chemical and physical
exergies of the combustion gases exiting the CC is shown in
Figure 3.9. An increase in GTIT leads to an increase in both
physical and chemical exergy. To explain this effect, we can

FIGURE 3.8 Exergy destruction rate (in

Exergy Destruction rate (%) Exergy destruction rate (MW)
absolute terms and as a percentage of the total
exergy destruction rate) in the CCPP and its
160 components (for RAC 17 and GTIT 1450 K).
140
Exergy destruction

120
100
80
60
40
20
0

FIGURE 3.9 Effect of GTIT on specific

chemical and physical exergy exiting the CC.
48 Exergy

FIGURE 3.10 Effect of GTIT on molar fractions of 0.8

combustion gases.

Molar fraction of combustion gases

0.7
XN2 XH O
2
0.6 XO2 XCO
2

0.5

0.4

0.3

0.2

0.1

0
1100 1200 1300 1400 1500
Gas turbine inlet temperature, T3 (K)

FIGURE 3.11 Effect of GTIT and degree

of supplemental firing on CCPP net power
output, for RAC 17.

consider the expression for specific physical exergy as shown in Figure 3.10. An increase in GTIT is observed to
follows: increase the molar fractions xCO2 and xH2 O . Since these
constituents have higher standard chemical exergies than the
exph;1 h3  h0  T0 s2  s0 other combustion products (see Table 3.2), an increase in




T3 P3 these two combustion products leads to an increase in the
Cp T3  T0  T0 ln  Rln chemical exergy of the mixture. Together, an increase in
T0 P0
GTIT increases the physical and chemical exergy at point 3,
decreasing the exergy destruction rate of the CC.
In this equation GTIT T3 and this expression increases The effect on combined cycle net power output of
when GTIT increases at a constant reference-environment varying the GTIT and the degree of supplemental firing is
temperature. To better understand the variation of chemical shown in Figure 3.11. The combined cycle net power
exergy, the combustion products are determined using output increases with both GTIT and fuel use in supple-
Equation 3.6 and the chemical exergy for the mixture is mental firing. At a fixed pressure ratio, a higher GTIT
found with Equation 3.18. The variations with GTIT of the results in a higher GT exhaust temperature and, as a result,
molar fractions of the combustion gases exiting the CC are more steam generation in the HRSG.
Chapter | 3 Chemical Exergy
The results discussed here focus on chemical exergy,
and thus emphasize the CC as well as the effect of GTIT on
combustion gas composition. Further details on the CCPP
are given elsewhere (Ahmadi et al., 2011a).
3.8 CLOSING REMARKS
In this chapter, the concept of chemical exergy is defined,
described, and applied. The chemical exergy of a substance
represents the maximum work obtainable from it in
a specified reference environment. The chemical exergy of
a compound or element is zero when it is in equilibrium
with substances in the reference environment. Chemical
exergy differs from the standard Gibbs energy of formation,
although it exhibits some similarities, and chemical exergy
is calculated using the Gibbs energy of formation. The
evaluation of chemical exergy is described for mixtures,
fuels, and other substances.
Chemical exergy is significant for analyses in which
there is chemical reaction (e.g., combustion) or phase
change. Thus chemical exergy is significant in analyses of
fossil fuel power generation, absorption, refrigeration, fuel
cell electrochemical processes, hydrogen production via
thermochemical water decomposition, water electrolysis,
and other processes. To enhance understanding of chemical
exergy, several illustrative examples and a case study
involving a CCPP are considered.
PROBLEMS
3.1 Using the partial pressures for the constituents in air
given in Table 3.1, find the standard chemical exergy
each constituent of air.
3.2 In Example 3.4, what is the effect of P1 and T1 on the
specific chemical exergy at point 3 and total exergy
destruction rate of the CC?
3.3 For the CCPP shown in Figure 3.4, what are the effect
of compressor pressure ratio and temperature at point
2 on (a) the specific chemical exergy at point 3 and (b)
the molar composition of combustion gases leaving
the CC?
3.4 In Example 3.4, with the same pressure and tempera-
ture at all points as shown in Figure 3.3, what are the
49
specific chemical exergy at point 3 and the exergy
destruction rate of the CC if natural gas (with a volu-
metric composition of CH4 96.57%, C2H6 2.63%,
C3H8 0.1%, and C4H10 0.7%) is injected into the
CC?
3.5 Biomass is a biological material formed from living or
recently living organisms, and is often viewed as
a renewable source of energy. As an energy source,
biomass can be used directly or converted into other
energy products such as biofuels. Calculate the
chemical exergy of the biomass pine sawdust using
the following composition data:
Biomass type Pine sawdust
Moisture content in biomass (by weight) 10%
Elemental analysis (dry basis by weight)
Carbon (C) 50.54%
Hydrogen (H) 7.08%
Oxygen (O) 41.11%
Sulfur (S) 0.57%
Also, determine the molar composition of the product
gases when pine sawdust is combusted according to the
following reaction:
Cx Hy Oz uH2 O gO2 3:76N2
/a CO2 bH2 O c N2
3.6 An engine uses methanol (CH3OH) as a fuel with
300% excess air. Air enters the engine at 1 bar and
25 C, and is mixed with fuel at 25 C before
combustion. Product gases leave the CC at 75 C.
Calculate (a) the molar composition of product gases,
(b) the chemical exergy of the product gases, and (c)
the exergy destruction and exergy efficiency for the
CC.
3.7 In Example 3.4, if combustion is not complete and
some CO is produced in the CC, what would be the
molar composition and chemical exergy of the product
gases?