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
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
Here, mi and mio are the chemical potentials of substance where moio and cio are the chemical potential and
i in its state and in the reference environment state, concentrations of component i, respectively, at the
respectively, and ni is the number of moles. The reference conditions. For a single-component system,
chemical potential mi is defined in terms of concentra- Equation 3.12 becomes the following:
tion c as follows:
c
mi moi RTlnci (3.11) Exch n m0 m00 RT0 ln (3.13)
c0
where moi is the standard state chemical potential.
Substitution of Equation 3.11 into Equation 3.10 yields:
3.3 CHEMICAL EXERGY FOR SOLID SPECIES
X X
Exch ni m0i m0i0 RT0 ni lnci =ci0 (3.12) The thermodynamic conditions of chemical species differ on
i i land relative to conditions in seawater. Mineral substances
Chapter | 3 Chemical Exergy 35
that exist on land can interact with water, oxygen, and other The chemical exergy of a mixture of N gases, in which all
species to make products. In this regard, the chemical exergy are constituents of the environment, can be obtained similarly.
of some substances from reference species dissolved in In this case, we can assume N different chambers (like the one
seawater is negative for some common elements on the land we already discussed). If each gas has a molar fraction of xk
surface such as CaCO3 and MgCO3. So, for elements such as and enters the chamber at T0 and with a partial pressure xk Po ,
Mg, Mn, and Co, the assumption that a solid reference then each gas exits at the same temperature and a partial
species exists on the land is unavoidable. More details about pressure xek . Summing for all constituents, the chemical
the chemical exergy for solid species are given in Szargut exergy per mole of the mixture can be calculated as follows:
et al. (1988). X e
x
exch RT0 xk ln k (3.18)
3.4 CHEMICAL EXERGY OF GAS MIXTURES 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
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
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
content. When the mole fraction of dry air (i.e., air without that relative humidity has a major effect on chemical exergy
H2O) is considered constant, the local atmospheric fractions of water vapor and N2.
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 3.6.2 Effect of Reference Environment
fractions are 0.78084 for N2, 0.20941 for O2, 0.000375 for Composition on Chemical Exergy
CO2, and 0.00934 for Ar (Szargut et al., 1988). According to
Szargut et al. (1988), the reference relative humidity is 0.7%, The reference environment is in stable equilibrium, with all
which means that at 25 C and 1 atm the molar fraction of parts at rest relative to one another. No chemical reactions
H2O is 0.02189. To compare the changes in chemical exergy, can occur between the environmental components. The
a relative deviation is defined as RD (exch,i /exch,i ref) 1. 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
3.6.1 Chemical Exergy Variation with system is zero when it is in equilibrium with the reference
environment. Chemical exergy is dependent on the selec-
Temperature and Moisture Content tion of a reference environment model, so chemical exergy
The variation of chemical exergy with ambient temperature values vary with the definition of the reference environ-
is shown in Figure 3.4. Here, we consider only the atmo- ment. The terms reference environment and natural envi-
spheric gases N2, O2, CO2, and water vapor. It is observed ronment are explained and differentiated in Section 2.8.1.
that, due to the variation of saturation pressure of water, Various reference environment models are explained in
water vapor plays a significant role in the variation of Chapter 2. As already explained, the atmosphere can serve
chemical exergy. As shown in this figure, other atmospheric as an appropriate reference state for only about 10 chemical
gases have the opposite tendency compared to water vapor. species. For other chemical species, convenient reference
This trend is mainly due to the proportionality of chemical species can be species that are most commonly found on
exergy with temperature, as given in Equation 3.5. As the surface of the earth (Szargut et al., 1988). However,
another example, the variation of chemical exergy for N2 defining the chemical composition of the earth is some-
with both ambient temperature and relative humidity is times difficult and can make consistent evaluations of
shown in Figure 3.5. It is seen that an increase in ambient exergy challenging.
temperature leads to an increase in chemical exergy of N2 Szargut et al. (1988) proposed that ions or compounds
and also at constant ambient temperature an increase in dissolved in seawater be used as the reference species for
relative humidity results in an increase in chemical exergy some elements. Hence, ionic reference species are adopted
of N2. The reason for this increase is that as the maximum when these elements appear in seawater in the form of
dilution with water vapor rises with temperature, the vari- monocharged or bicharged ions. The average values of
ation with relative humidity increases. The effect of vari- mass fraction of elements in seawater from different sour-
ation of chemical exergy with relative humidity of some ces are listed by Szargut et al. (1988). Various different
atmospheric gases is shown in Figure 3.6. It is concluded models for the reference environment have been proposed,
H2 O N2
70% relative humidity. The relative deviation in percentage is
60 O2 CO
O2 relative to the values at reference conditions of 25 C, 1 atm,
and 70% relative humidity.
40
20
-20
-40
-30 -20 -10 0 10 20 30 40
Ambient temperature (C)
42 Exergy
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
-10
0.2 0.4 0.6 0.8 1
Relative humidity,
Chapter | 3 Chemical Exergy 43
To calculate the specific chemical exergy of Si(s), the 3.7 CASE STUDY: CCPP WITH
exergy balance of the reaction of formation of the SUPPLEMENTAL FIRING
reference species, SiO2(s), is required. The reaction
is as follows: CCPPs have recently received considerable attention due
to their relatively high efficiencies, low pollutant and
Sis O2;g /SiO2;s greenhouse gas emissions, and operational flexibility. In
this case study, we consider a common CCPP, the gas-
steam combined cycle (see Figure 3.7), which is comprised
Using Equation 3.7 and knowing that DG0SiO2 of a GT cycle (topping cycle) and a steam turbine (ST)
856:67 kJ=mol and ex0ch;O2 3:97 kJ=mol from cycle (bottoming cycle) coupled through a heat recovery
Table 3.2: steam generator (HRSG). The cycle includes supplemental
firing. The case study illustrates how chemical exergy is
ex0ch;Si ex0ch;SiO2 DG0SiO2 ex0ch;O2 calculated and describes its relation to cycle design
parameters such as cycle exergy efficiency and exergy
1:861 856:67 3:97 854:56 kJ=mol destruction rate.
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.
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)
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.
TABLE 3.5 Expressions for Exergy Destruction Rate and Exergy Efficiency for CCPP Component
_ 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 efficiency improvements can be sought and alternative
and degree of supplemental firing. 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
3.7.4 Results understand how both physical and chemical exergy at the
Exergy destructions for the components in the CCPP are exit of the CC (point 3 in Figure 3.7) vary with operating
shown in Figure 3.8. The exergy analysis results demon- and design parameters. According to Figure 3.8, the exergy
strate that, for the operating conditions considered, the CC destruction rate for the CC is strongly dependent on the
incurs the most significant exergy destruction in the CCPP. exergy at point 3, and increasing this exergy leads to
This result is attributable to the significant irreversibilities a decrease in the total exergy destruction rate of the CC for
associated with chemical reaction and heat transfer across a constant compressor pressure ratio.
the large temperature differences between the burner gases The effect of GTIT on both chemical and physical
and the working fluid. The exergy destruction with exergies of the combustion gases exiting the CC is shown in
combustion is linked to the nature of the process considered Figure 3.9. An increase in GTIT leads to an increase in both
here and, to reduce this exergy destruction significantly, physical and chemical exergy. To explain this effect, we can
120
100
80
60
40
20
0
0.5
0.4
0.3
0.2
0.1
0
1100 1200 1300 1400 1500
Gas turbine inlet temperature, T3 (K)
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 49
The results discussed here focus on chemical exergy, specific chemical exergy at point 3 and the exergy
and thus emphasize the CC as well as the effect of GTIT on destruction rate of the CC if natural gas (with a volu-
combustion gas composition. Further details on the CCPP metric composition of CH4 96.57%, C2H6 2.63%,
are given elsewhere (Ahmadi et al., 2011a). C3H8 0.1%, and C4H10 0.7%) is injected into the
CC?
3.5 Biomass is a biological material formed from living or
3.8 CLOSING REMARKS recently living organisms, and is often viewed as
In this chapter, the concept of chemical exergy is defined, a renewable source of energy. As an energy source,
described, and applied. The chemical exergy of a substance biomass can be used directly or converted into other
represents the maximum work obtainable from it in energy products such as biofuels. Calculate the
a specified reference environment. The chemical exergy of chemical exergy of the biomass pine sawdust using
a compound or element is zero when it is in equilibrium the following composition data:
with substances in the reference environment. Chemical
exergy differs from the standard Gibbs energy of formation, Biomass type Pine sawdust
although it exhibits some similarities, and chemical exergy
is calculated using the Gibbs energy of formation. The Moisture content in biomass (by weight) 10%
evaluation of chemical exergy is described for mixtures, Elemental analysis (dry basis by weight)
fuels, and other substances. Carbon (C) 50.54%
Chemical exergy is significant for analyses in which
there is chemical reaction (e.g., combustion) or phase Hydrogen (H) 7.08%
change. Thus chemical exergy is significant in analyses of Oxygen (O) 41.11%
fossil fuel power generation, absorption, refrigeration, fuel Sulfur (S) 0.57%
cell electrochemical processes, hydrogen production via
thermochemical water decomposition, water electrolysis,
and other processes. To enhance understanding of chemical Also, determine the molar composition of the product
exergy, several illustrative examples and a case study gases when pine sawdust is combusted according to the
involving a CCPP are considered. following reaction: