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 ¼ 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 ¼
exch þ xexch þ yex  x þ 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 ¼ HHVðT0 ; P0 Þ
exch term are evaluated via the temperature, the pressure, and

  the composition of the reference environment. The
1 y
 T0 sF þ x þ y sO2  xsCO2  sH2 O maximum theoretical value for the work based on Equation
4 2 ðT0 ;P0 Þ 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
þ xexch
O2 þ yex  x þ 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 ¼ hF þ x þ y hO2  xhCO2  yhH2 O
4 2
g ¼ h  T s, Equation 3.29 can be alternatively expressed 
 
1 1
as follows:  T0 sF þ x þ y sO2  xsCO2  ysH2 O
4 2

 
1 y (3.32)
exch
F ¼ gF þ x þ y gO2  xgCO2  gH2 O
4 2 ðT0 ;P0 Þ Knowing that si ðT0 ; xi P0 Þ ¼ si ðT0 ; P0 Þ  Rlnxi (Bejan


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

 
(3.30) 1 1
exch ¼ hF þ x þ y hO2  xhCO2  yhH2 O
4 2 ðT0 ;P0 Þ
To assist in determining the chemical exergy of fuels, 
 
1 1
Szargut et al. (1988) provided values of the exergy to  T0 sF þ x þ y sO2  xsCO2  ysH2 O
energy ratio, F ¼ exf =LHV. For most hydrocarbons, this 4 2 ðT0 ;P0 Þ
" #
ratio is near unity. For common gaseous fuels, for instance, 1
xþ4y
ðxO2 Þ
the ratio of chemical exergy to lower heat value for þ RT0 ln y

methane and hydrogen are FCH1 ¼ 1:06, and ðxCO2 Þx ðxH2 O Þ4

FH2 ¼ 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 ¼ 1:0401 þ 0:1728 þ 0:0432 1 y
a a exch ¼ gF þ x þ y gO2  xgCO2  gH2 O

 4 2 ðT0 ;P0 Þ
g b " #
þ 0:2169 1  2:062 (3.31) ðxO2 Þ xþ14y
a a þ RT0 ln y
b b g ðxCO2 Þx ðxH2 O Þ4
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 lþ1 lþ1
FIGURE 3.3 CC used in GT cycle.
0:0003 þ l 0:019 þ 2l
Example 3.4: The combustion chamber (CC) is a major xCO2 ¼ ; xH2 O ¼
lþ1 lþ1
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 ¼ 550 K and P1 ¼ 10 bar follows:
and the combustion gases exit at T3 ¼ 1400 K. The molar
composition of air is 0.7748 for N2, 0.2059 for O2,
Q_ CV  W_ CV þ n_ F hF þ n_ a ha  n_ p hp ¼ 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 ð0:02l  LHVÞ
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 þ ha þ l hF  ð1 þ lÞhP ¼ 0
point 3.
3. For a reference state of T0 ¼ 298.15 K and P0 ¼
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 ¼ 550 K and T3 ¼ 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 ¼ ½0:7748hN2 þ 0:2059hO2 þ 0:0003hCO2
air ratio l as the following:
n_ F þ 0:019hH2 O at T1
¼ l
n_ a

1
So: hP ¼ ½0:7748hN2 þ ð0:2059  2lÞhO2
lþ1
n_ P n_ a þ n_ F
¼ ¼ lþ1
n_ a n_ a
þ ð0:0003 þ lÞhCO2 þ ð0:019 þ lÞhH2 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 þ ½0:7748 N2 þ 0:2059 O2 þ 0:0003 CO2
þ 0:019 H2 O / ½l þ 1½xN2 N2 þ xO2 O2 0:7748DhN2 þ 0:2059DhO2 þ 0:0003DhCO2 þ 0:019DhH2 O
l ¼
þ xCO2 CO2 þ xH2 O H2 O hF  0:02LHV  ð2hO2 þ hCO2 þ 2hH2 O ÞðT4 Þ
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 ¼ 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 ¼ 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 ¼ 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 ¼ xv P0 ¼ ð0:0939Þð1:013 barÞ ¼ 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 ¼ ðh3  h0 Þ  T0 ðs3  s0 Þ Pv ¼ xv P0 ¼ nv =ð0:9061 þ nv Þ  P0 , where nv is


 the amount of water vapor. Hence, 0:0317 bar ¼
T3 P3
¼ Cp ðT3  T0 Þ  T0 Cp ln  Rln ðnv  1:013 barÞ=ð0:9061 þ nv Þ, which yields nv ¼
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 ¼ P1 ¼ 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 ¼ 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 ¼ 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 ¼ ð1  0:06583Þ  22:95 þ 0:06583 
X X 18
exch;3 ¼ xk exkch þ RT0 xk lnxk
¼ 24:32 kJ=kg
¼ ð0:1224  3970 þ 0:0381  19870
þ 0:0939  9490 þ 0:745  720Þ Here, the first term is the percentage of dry
þ ð8:314  298:15  ½0:1224lnð0:1224Þ combustion gases multiplied by the specific chem-
ical exergy obtained from Part 2, and the second term
þ 0:0381lnð0:0381Þ þ 0:0939lnð0:0939Þ is the product of the molar fraction of liquid water
þ 0:745lnð0:745ÞÞ due to the condensation and specific chemical exergy
kJ kJ of liquid water.
¼ 632:1 ¼ 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 ¼ exch;3 þ exph;3 ¼ 24:32 þ 933:1 ¼ 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 ¼ ¼ 16 ¼ 0:0393/m_ a ¼ 71:42 _
ExD ¼ 0:02  m_ f  LHV 1 
n_ a m_ a s 1400
29 þ 71:42  281:7 þ 1:5  1:06  50;147:5
 ð1:5 þ 71:42Þ  957:42 ¼ 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 ¼ F  LHV follows:

_ 3
Ex
¼
_ _ _ Q
Ex1 þ Exf þ Ex
ð1:5 þ 71:42Þ  957:42
¼
 ¼ 69%
298:15
71:42  281:7 þ 1:5  1:06  50147:5 þ 0:02  m_ f  LHV 1 
1400

where FCH4 ¼ 1:06 and LHV CH4 ¼ 802;361 kJ=kmol Part 4:

¼ 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 ¼ 594
specific exergy at point 1: K and T3 ¼ 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 ¼ ðh1  h0 Þ  T0 ðs1  s0 Þ


 et al. (2008), as shown in the following tabulation:
T1 P1
¼ Cp ðT2  T0 Þ  T0 Cp ln  Rln
T0 P0 Component N2 CO2 H2O O2
kJ
¼ 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

_ Qþ
Ex m_ i exi ¼ _ w þ Ex
m_ e exe þ 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  þ m_ 1 ex1 þ m_ f exf ¼ ðm_ f þ m_ 1 Þex3 (Ertesvag, 2007). The concentration of gases other than
T3
water vapor can be considered constant. Therefore,
þ Ex _ D
composition changes are attributable to the moisture