Exergy of Fuels
Exergy of Fuels
Exergy of Fuels
products at T0 and P0
Qin
T0
Figure 13-8: The reversible conversion of fuel to products at the dead state.
The system is chosen so that any heat that is exchanged between the system and the surroundings
crosses the boundary of the system at the temperature of the surroundings. Therefore, there is no
exergy flow to or from the system associated with the heat transfer. The combustion products
exit the system at the dead state. These products must be in complete equilibrium with the
surroundings in order to have no exergy. Therefore, the products are at the same temperature,
pressure as the surroundings. The products must also have the same composition as the
surroundings so that they have no chemical potential relative to the dead state. The only nonE18-1
THERMODYNAMICS, S.A. Klein and G.F. Nellis, Cambridge University Press, 2011
zero exergy flow out of the system is the work. If no exergy is destroyed in the conversion
process (i.e., the process is reversible), then the exergy of the fuel entering the system must be
equal to the work that is produced, which is the maximum possible work.
The maximum work (and therefore, the exergy of the fuel) can be determined using energy and
entropy balances on the system shown in Figure 13-8. An energy balance provides:
H R Qin H P Wout
(13-73)
where HR and HP are the enthalpies of the reactants and products, respectively. In this analysis,
both the reactants and products are at the dead state temperature. Kinetic and potential energy
terms do not appear in Eq. (13-73) because the fuel and air are provided to the system with
negligible velocity and elevation and the products exit at the dead state. The heat transfer to the
system can be determined from an entropy balance on the reversible system:
SR
Qin
SP
T0
(13-74)
(13-75)
Substituting Eq. (13-75) into Eq. (13-73) provides the maximum possible work (and thus the
exergy of the fuel):
X fuel Wout H R H P T0 S R S P
(13-76)
Note that the value of the quantity H R H P will be between the lower and higher heating
values of the fuel if T0 = Tref = 25C. The exact value of
HR HP
definition of the dead state. The product T0 S R S P is much smaller than the heating value for
most fuels. Therefore, if you read no further, it should at least be clear that the specific exergy of
a fuel at dead-state conditions is approximately equal to the heating value per mole of fuel:
x fuel HV
(13-77)
where HV is a value between the lower and higher heating values of the fuel.
H R ni hi ,0
i 1
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(13-78)
THERMODYNAMICS, S.A. Klein and G.F. Nellis, Cambridge University Press, 2011
H P n j h j ,0
(13-79)
j 1
where NP is the number of products, n j is the stoichiometric coefficient for product j, and h j ,0 is
the molar specific enthalpy of product j at the dead state.
The reactants and products involved in combustion reactions are generally either gases that can
be modeled according to the ideal gas law or liquids and solids that can be considered to be
incompressible. The molar specific enthalpy of these substances is independent of pressure and
therefore the dead state values of HR and HP in Eqs. (13-78) and (13-79) can be readily evaluated
using the dead state temperature.
The entropy of the reactants per mole of fuel is calculated according to:
NR
S R ni si ,0
(13-80)
i 1
where si ,0 is the molar specific entropy of reactant i at the dead state condition. If reactant i is a
pure substance as it enters the reactor, then the molar specific entropy should be evaluated using
the total pressure for this reactant. If reactant i is a component in an ideal gas mixture, then the
specific entropy should be evaluated at its partial pressure, as discussed in Section 11.2. The
entropy of the products is determined in a similar way:
NP
S P n j s j ,0
(13-81)
j 1
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THERMODYNAMICS, S.A. Klein and G.F. Nellis, Cambridge University Press, 2011
Based on this discussion, the quantity s j ,0 in Eq. (13-81) is the molar specific entropy of product
j at the temperature and partial pressure of that component as it exists in the surroundings. In
addition, the quantity si ,0 in Eq. (13-80) for every reactant except the fuel must also be evaluated
at the temperature and partial pressure of that component as it exists in the surroundings.
Clearly, it is necessary to know the composition of the surroundings (as well as its temperature
and pressure). Table 13-5 provides the molar composition of dry air in the surroundings,
assuming a mean mole fraction of 0.0004 for carbon dioxide. (Note that the mole fraction of
carbon dioxide in the surroundings continues to slowly increase.) Of course, the surroundings
will also always contain some water vapor as well. Table 13-5 also provides the composition of
the surroundings including water vapor if the environment is at the dead state temperature and
pressure (25C and 1 atm) and 50% relative humidity. The mole fractions in this table can be
used to calculate the partial pressure of combustion products at the dead state.
Table 13-5: Composition of air in the surroundings (Lemmon et al., 2000).
Gas
Mole fraction in dry air
Mole fraction in air at 25C, 1 atm
and 50% relative humidity
nitrogen
0.7808
0.7686
oxygen
0.2095
0.2062
argon
0.0093
0.0092
carbon dioxide
0.0004
0.0004
water vapor
0
0.0156
The methodology will be applied to calculate the exergy of methane assuming surroundings at T0
= 25C, P0 = 1 atm, and 50% relative humidity.
$UnitSystem SI Molar Radian J K Pa
T_o=converttemp(C,K,25[C])
P_o=1 [atm]*convert(atm,Pa)
y_N2_o=0.7686 [-]
y_O2_o=0.2062 [-]
y_Ar_o=0.0093 [-]
y_CO2_o=0.0004 [-]
y_H2O_o=0.0156 [-]
We start by specifying a basis of one mole of methane and balancing the reaction for complete
combustion. We assume that the surrounding air is used as the oxidizer and include some
amount of excess air. For example, the reaction with ea = 50% excess air, using the composition
of air with 50% relative humidity listed in Table 13-5, can be considered. Start with the
stoichiometric reaction:
CH 4 as y N2 ,0 N 2 yO2 ,0 O 2 y Ar ,0 Ar yCO2 ,0 CO 2 yH 2O ,0 H 2 O
bs CO 2 cs H 2 O d s N 2 es Ar
(13-82)
1 as yCO2 ,0 bs
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(13-83)
THERMODYNAMICS, S.A. Klein and G.F. Nellis, Cambridge University Press, 2011
4 2 as yH 2O ,0 2 cs
(13-84)
2 as yO2 ,0 2 as yCO2 ,0 as yH 2O ,0 2 bs cs
(13-85)
2 as y N2 ,0 2 d s
(13-86)
as y Ar ,0 es
(13-87)
Equations (13-83) through (13-87) provide the coefficients of the stoichiometric reaction.
"Balance stoichiometric reaction"
1+a_s*y_CO2_o=b_s
4+2*a_s*y_H2O_o=2*c_s
2*a_s*y_O2_o+2*a_s*y_CO2_o+a_s*y_H2O_o=2*b_s+c_s
2*a_s*y_N2_o=2*d_s
a_s*y_Ar_o=e_s
"balance C's"
"balance H's"
"balance O's"
"balance N's"
"balance Ar's"
The actual reaction has 50% excess air; therefore, it has 1.5x as many moles of air as the
stoichiometric reaction, Eq. (13-82).
CH 4 a y N2 ,0 N 2 yO2 ,0 O 2 y Ar ,0 Ar yCO2 ,0 CO 2 yH 2O ,0 H 2O
b CO 2 c H 2O d N 2 e Ar f O 2
(13-88)
where
a 1 ea as
(13-89)
Balancing carbon, hydrogen, oxygen, nitrogen, and argon atoms in Eq. (13-88) leads to:
1 a yCO2 ,0 b
(13-90)
4 2 a yH 2O ,0 2 c
(13-91)
2 a yO2 ,0 2 a yCO2 ,0 a yH 2O ,0 2 b c 2 f
(13-92)
2 a y N2 ,0 2 d
(13-93)
a y Ar ,0 e
(13-94)
Equations (13-89) through (13-94) provide the coefficients of the actual reaction, Eq. (13-88).
"Balance actual reaction"
ea=0.5 [-]
a=(1+ea)*a_s
"excess air"
"amount of air, based on excess air"
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THERMODYNAMICS, S.A. Klein and G.F. Nellis, Cambridge University Press, 2011
1+a*y_CO2_o=b
4+2*a*y_H2O_o=2*c
2*a*y_O2_o+2*a*y_CO2_o+a*y_H2O_o=2*b+c+2*f
2*a*y_N2_o=2*d
a*y_Ar_o=e
"balance C's"
"balance H's"
"balance O's"
"balance N's"
"balance Ar's"
The molar specific enthalpy of each of the substances involved in the reaction ( hCH 4 ,0 , hN2 ,0 ,
hO2 ,0 , hAr ,0 , hCO2 ,0 , and hH 2O ,0 ) are computed at the dead state temperature. The enthalpy of the
(13-96)
The molar specific entropy of the methane ( sCH 4 ,0 ) is computed at the dead state temperature and
pressure.
"molar specific entropies"
s_bar_CH4_o=entropy(CH4,T=T_o,P=P_o)
"methane"
The molar specific entropies of each of the other substances involved in the reaction ( sN2 ,0 , sO2 ,0 ,
s Ar ,0 , sCO2 ,0 , and sH 2O ,0 ) are computed at the dead state temperature and the partial pressure that
these substances have in the surroundings (i.e., the products of their equilibrium concentrations
and the dead state pressure).
s_bar_N2_o=entropy(N2,T=T_o,P=P_o*y_N2_o)
s_bar_o2_o=entropy(O2,T=T_o,P=P_o*y_o2_o)
s_bar_Ar_o=entropy(Ar,T=T_o,P=P_o*y_Ar_o)
s_bar_CO2_o=entropy(CO2,T=T_o,P=P_o*y_CO2_o)
s_bar_H2O_o=entropy(H2O,T=T_o,P=P_o*y_H2O_o)
"nitrogen"
"oxygen"
"argon"
"carbon dioxide"
"water vapor"
The entropy of the reactants and products of Eq. (13-88) are computed according to:
S R sCH 4 ,0 a y N2 ,0 sN2 ,0 a yO2 ,0 sO2 ,0 a y Ar ,0 s Ar ,0 a yCO2 ,0 sCO2 ,0 a yH 2O ,0 sH 2O ,0 (13-97)
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THERMODYNAMICS, S.A. Klein and G.F. Nellis, Cambridge University Press, 2011
(13-98)
S_R=s_bar_CH4_o+a*y_N2_o*s_bar_N2_o+a*y_o2_o*s_bar_o2_o&
+a*y_Ar_o*s_bar_Ar_o+a*y_CO2_o*s_bar_CO2_o+a*y_H2O_o*s_bar_H2O_o
"entropy of reactants per mole of CH4"
S_P=b*s_bar_CO2_o+c*s_bar_H2O_o+d*s_bar_N2_o+e*s_bar_Ar_o+f*s_bar_o2_o
"entropy of products per mole of CH4"
"exergy of fuel"
"on a mass basis"
which leads to x fuel = 833,100 kJ/kmol (51,930 kJ/kg). Notice that the specific exergy of the fuel
lies between the lower and higher heating values for methane, provided in Table 13-3.
The value of the exergy of the fuel is independent of the amount of excess air. For example,
reduce the value of ea in the EES code to ea = 0 (i.e., use a stoichiometric amount of air) and the
calculated value of x fuel will not change. This result occurs because the state of each of the
reactants (other than the fuel) and the products are identical; the specific enthalpy and specific
entropy of each substance are evaluated at the dead state temperature and the partial pressure that
the component has in the surroundings. Therefore, only those substances that are actually
involved in the reaction will result in a difference between the enthalpy of the reactants relative
to the products, the quantity HR - HP in Eq. (13-76), and a difference between the entropy of the
reactants relative to the products, the quantity SR - SP in Eq. (13-76). With this in mind, the
chemical reaction used to evaluate the exergy of a fuel can be greatly simplified. It is not
necessary to consider anything but the fuel, the oxygen with which it reacts, and the resulting
products (i.e., it is not necessary to consider the argon, nitrogen, or excess oxygen):
CH 4 2 O 2 CO 2 2 H 2 O
(13-99)
Every term in Eq. (13-88) that does not appear in Eq. (13-99) is related to a substance that does
not change either its molecular structure or its state between the inlet and exit state and therefore
does not affect the fuel exergy. Using Eq. (13-99), the enthalpies of the reactants and products
per mole of fuel are given by:
H R hCH 4 ,0 2 hO2 ,0
(13-100)
H P hCO2 ,0 2 hH 2O ,0
(13-101)
and the entropies of the reactants and products per mole of fuel are given by:
S R sCH 4 ,0 2 sO2 ,0
(13-102)
S P sCO2 ,0 2 sH 2O ,0
(13-103)
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THERMODYNAMICS, S.A. Klein and G.F. Nellis, Cambridge University Press, 2011
Note that the specific entropy of each ideal gas product is evaluated at the dead state temperature
and the partial pressure at which that gas exists in the environment. The exergy of fuel is again
computed using Eq. (13-76).
H_R_2=h_bar_CH4_o+2*h_bar_o2_o
H_P_2=h_bar_CO2_o+2*h_bar_H2O_o
S_R_2=s_bar_CH4_o+2*s_bar_o2_o
S_P_2=s_bar_CO2_o+2*s_bar_H2O_o
x_fuel_2=H_R_2-H_P_2-T_o*(S_R_2-S_P_2)
x_fuel_m_2=X_fuel_2/MolarMass(CH4)
The simplified reaction in Eq. (13-99) results in an identical solution, x fuel = 833,100 kJ/kmol
(51,930 kJ/kg). The exergy of the fuel does depend on the relative humidity of the surroundings
as this will change the concentrations of the components in the surroundings slightly. However,
this dependence is very small.
building
Tbldg = 22C
Qout
air
Tin = -10C
Pin = 1 atm
furnace
methane at Tin
The furnace combusts methane with 200% excess dry air (ea = 2). The air and methane enter the
combustor at Tin = -10C and Pin = 1 atm. The furnace provides heat transfer to the building,
which is maintained at Tbldg = 22C. The combustion products leave at Tout = 150C and Pout = 1
atm.
a.) Determine the first law efficiency of the furnace based on the higher and lower heating values
of the fuel.
The inputs are entered in EES.
$UnitSystem SI Molar Radian J K Pa
T_in=converttemp(C,K,-10 [C])
P_in=1 [atm]*convert(atm,Pa)
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THERMODYNAMICS, S.A. Klein and G.F. Nellis, Cambridge University Press, 2011
T_bldg=converttemp(C,K,22 [C])
T_out=converttemp(C,K,150 [C])
P_out=1 [atm]*convert(atm,Pa)
ea=2 [-]
"building temperature"
"exit temperature"
"exit pressure"
"excess air"
(1)
The following equations balance carbon, hydrogen, oxygen, and nitrogen in Eq. (1):
1 bs
4 2 cs
as 0.21 2 2 bs cs
as 0.79 2 2 d s
"Balance stoichiometric reaction"
1=b_s
4=2*c_s
2*0.21*a_s=2*b_s+c_s
2*0.79*a_s=2*d_s
"balance C's"
"balance H's"
"balance O's"
"balance N's"
Balancing carbon, hydrogen, oxygen, and nitrogen in Eq. (2) leads to:
1 b
4 2c
a 0.21 2 2 b c 2 e
a 0.79 2 2 d
"Balance actual reaction"
a=(1+ea)*a_s
"excess air"
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(2)
THERMODYNAMICS, S.A. Klein and G.F. Nellis, Cambridge University Press, 2011
1=b
4=2*c
2*0.21*a=2*b+c+2*e
2*0.79*a=2*d
"balance C's"
"balance H's"
"balance O's"
"balance N's"
In order to carry out an energy balance on the furnace, it is necessary to determine the phase of
the water in the products. Assuming no condensation, the mole fraction of water vapor in the
combustion products is:
yv
c
bcd e
The dew point temperature of the combustion products (Tdp) is the saturation temperature of
water at its partial pressure, obtained using the T_sat function in EES.
y_v=c/(b+c+d+e)
P_v=y_v*P_out
T_dp=T_sat(Water,P=P_v)
T_dp_C=converttemp(K,C,T_dp)
Solving these equations results in Tdp = 38.6C. The water in the products must be entirely in the
vapor phase since the outlet temperature is above the dew point temperature.
The molar specific enthalpy of the reactants ( hCH 4 ,in , hO2 ,in , and hN2 ,in ) are computed. The
enthalpy of the reactants per mole of fuel is obtained from:
H R hCH 4 ,in as 0.21 hO2 ,in as 0.79 hN2 ,in
h_bar_CH4_in=enthalpy(CH4,T=T_in)
"molar specific enthalpy of methane entering"
h_bar_O2_in=enthalpy(O2,T=T_in)
"molar specific enthalpy of oxygen entering"
h_bar_N2_in=enthalpy(N2,T=T_in)
"molar specific enthalpy of nitrogen entering"
H_R=h_bar_CH4_in+0.21*a*h_bar_O2_in+0.79*a*h_bar_N2_in "enthalpy of reactants per mole of fuel"
The molar specific enthalpy of the products ( hCO2 ,out , hH 2O ,out , hN2 ,out , and hO2 ,out ) are computed.
The enthalpy of the products per mole of fuel is obtained from:
H P b hCO2 ,out c hH 2O ,out d hN2 ,out e hO2 ,out
h_bar_CO2_out=enthalpy(CO2,T=T_out)
"molar specific enthalpy of CO2 leaving"
h_bar_H2O_out=enthalpy(H2O,T=T_out)
"molar specific enthalpy of H2O leaving"
h_bar_N2_out=enthalpy(N2,T=T_out)
"molar specific enthalpy of N2 leaving"
h_bar_O2_out=enthalpy(O2,T=T_out)
"molar specific enthalpy of O2 leaving"
H_P=b*h_bar_CO2_out+c*h_bar_H2O_out+d*h_bar_N2_out+e*h_bar_O2_out
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THERMODYNAMICS, S.A. Klein and G.F. Nellis, Cambridge University Press, 2011
"enthalpy of products per mole of fuel"
An energy balance on the furnace (on a per mole of fuel basis) provides:
H R Qout H P
H_R=Q_out+H_P
The lower and higher heating values of methane (LHV and HHV) are obtained from Table 13-3
and converted to a molar basis.
LHV=50032 [kJ/kg]*convert(kJ/kg,J/kg)*MolarMass(CH4)
HHV=55516 [kJ/kg]*convert(kJ/kg,J/kg)*MolarMass(CH4)
The first law efficiency of the furnace based on the lower and higher heating values are
calculated according to:
st
law, LHV
st
law, HHV
Qout
LHV
Qout
HHV
eta_1stlaw_furnace_LHV=Q_out/LHV
eta_1stlaw_furnace_HHV=Q_out/HHV
From a first law standpoint, this furnace is very efficient: 1st law,LHV = 82.42% and 1st law, HHV =
74.3%.
b.) Determine the Second Law efficiency of the furnace.
The exergy of methane was computed in Section 13.5.2, Xfuel = 8.331x108 J/kmol. The exergy of
the heat produced by the furnace is computed according to:
T
X Qout Qout 1 0
Tbldg
where T0 is the dead state temperature. In this problem, the dead state temperature corresponds
to the outdoor air temperature, T0 = Tin. The Second Law efficiency of the furnace is given by:
2
T_o=T_in
x_Q_out=Q_out*(1-T_o/T_bldg)
nd
law
X Qout
X fuel
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THERMODYNAMICS, S.A. Klein and G.F. Nellis, Cambridge University Press, 2011
x_fuel=8.331e8 [J/kmol]
eta_2ndlaw_furnace=x_Q_out/x_fuel
"exergy of fuel"
"Second Law efficiency of the furnace"
The Second Law efficiency of the furnace is extremely low; 2nd law = 8.61%. This result is
sobering. However it does indicate that, from a thermodynamic perspective, it is possible to
significantly reduce the amount of fuel consumed for house heating. Methods for increasing the
efficiency with gas-fired heat pumps have been developed, but they have not been found to be
economically viable thus far.
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