Gestão de Sistemas Energéticos

2015/2016
Exergy Analysis

Prof. Tânia Sousa

taniasousa@ist.utl.pt
 Exergy

• Exergy is …
• Thermomechanical exergy: if temperature and/or
pressure of a system differ from that of the
environment;
• Chemical exergy – if there is a composition difference
between the system and environment;
 Evaluating Chemical Exergy

• The exergy reference environment (the Earth and its

atmosphere)
– Environmental temperature T0 and pressure p0.
– Set of reference substances with concentrations closely
corresponding to the chemical makeup of the natural
environment.
• Reference substances may include
– Gaseous components of the atmosphere: N2, O2, CO2,
H2O(g), and other gases.
– Solid substances from the Earth’s crust.
– Substances from the oceans.
 Conceptualizing Chemical Exergy

CaHbOc enters the control volume

at T0, p0.

O2 and CO2, H2O(g) enter and exit

the control volume at T0 and their
respective partial pressures.

The ideal gas model applies to O2,

CO2, and H2O(g).
 Conceptualizing Chemical Exergy

Negligible kinetic and potential

energy effects

Heat transfer between the control

volume and environment occurs
only at temperature T0

Steady state

The chemical exergy per mole of

CaHbOc, ech, is the maximum
theoretical value of Wcv/nF
 Conceptualizing Chemical Exergy

The logarithmic term typically

contributes only a few percent to
the chemical exergy magnitude
 Example

Compute the exergy of methane, CH4, when T0 =

298.15 K (25oC), p0 = 1 atm.
 Example

Compute the exergy of methane, CH4, when T0 =

298.15 K (25oC), p0 = 1 atm.

e ch  g F  2 gO2  gCO 2  2 g H 2O(g)  R T0 ln


   e 2
yO2

   
 e  e
 yCO 2 yH 2O
2
 Example

Compute the exergy of methane, CH4, when T0 =

298.15 K (25oC), p0 = 1 atm.

gf,oCH 4  50,790 kJ/kmol gf,oCO 2  394,380 kJ/kmol

gf,oO2  0 kJ/kmol gf,oH 2O(g)  228,590 kJ/kmol

 Example

Compute the exergy of methane, CH4, when T0 =

298.15 K (25oC), p0 = 1 atm.

Standard Molar Chemical Exergy, ech (kJ/kmol), of Selected Substances at 298 K and p0
Substance Formula Model Ia Model IIb
Oxygen O2(g) 3,950 3,970
Carbon dioxide CO2(g) 14,175 19,870
Water H2O(l) 45 900
Hydrogen H2(g) 235,250 236,100
Methane CH4(g) 824,350 831,650
Octane C8H18(l) – 5,413,100
Ethanol C2H5OH(l) 1,342,085 1,357,700

kJ
e ch
 830,174
kmol
 Example

What is the pure CO2 exergy, when T0 = 298.15 K

(25oC), p0 = 1 atm?
 Example

Compute the exergy of pure CO2, when T0 = 298.15

K (25oC), p0 = 1 atm.
 Example

Compute the exergy of CO2, when T0 = 298.15 K

(25oC), p0 = 1 atm.

Standard Molar Chemical Exergy, ech (kJ/kmol), of Selected Substances at 298 K and p0
Substance Formula Model Ia Model IIb
Oxygen O2(g) 3,950 3,970
Carbon dioxide CO2(g) 14,175 19,870
Water H2O(l) 45 900
Hydrogen H2(g) 235,250 236,100
Methane CH4(g) 824,350 831,650
Octane C8H18(l) – 5,413,100
Ethanol C2H5OH(l) 1,342,085 1,357,700

 1  Applies also to other gases

e ch
 R T0 ln  e  in the environment
 ( yCO ) 
 2 
kJ
e  20,108
ch

kmol
 Example

What about the exergy of H2O, when T0 = 298.15 K

(25oC), p0 = 1 atm?
 Example

What about the exergy of H2O, when T0 = 298.15 K

(25oC), p0 = 1 atm?
 Example

What about an ideal mixture of gases with gases

that are present in the environment and with molar
fractions of yi when T0 = 298.15 K (25oC), p0 = 1 atm?
 Example

What about an ideal mixture of gases present in the

environment when T0 = 298.15 K (25oC), p0 = 1 atm?
Conceptualizing Chemical Exergy
 Exergy Balances to Reacting Systems

• What is the exergy balance to the reversible steady-

state combustion of CaHb?
 Standard Chemical Exergy

• The standard exergy value of CaHb is

 Example

Compute the exergy of methane, CH4, when T0 =

298.15 K (25oC), p0 = 1 atm.
gfo (CH4)=
-50,79kJ/kmol

Thermochemical Properties of Selected Substances at 298K and 1 atm

Heating Values
Enthalpy of Gibbs Function Absolute
Formation, of Formation, Entropy,
Higher, Lower,
Molar Mass, hfo g fo so HHV LHV
Substance Formula M (kg/kmol) (kJ/kmol) (kJ/kmol) (kJ/kmol∙K) (kJ/kg) (kJ/kg)
Carbon C(s) 12.01 0 0 5.74 32,770 32,770
Hydrogen H2(g) 2.016 0 0 130.57 141,780 119,950
Nitrogen N2(g) 28.01 0 0 191.50 – –
Oxygen O2(g) 32.00 0 0 205.03 – –
Carbon Monoxide CO(g) 28.01 –110,530 –137,150 197.54 – –
Carbon dioxide CO2(g) 44.01 –393,520 –394,380 213.69 – –
Water H2O(g) 18.02 –241,820 –228,590 188.72 – –
Water H2O(l) 18.02 –285,830 –237,180 69.95 – –
Hydrogen peroxide H2O2(g) 34.02 –136,310 –105,600 232.63 – –
Ammonia NH3(g) 17.03 –46,190 –16,590 192.33 – –
 Example

The exergy of methane, CH4, when T0 = 298.15 K

(25oC), p0 = 1 atm.

=831,680kJ/kmol=51980kJ/kg

Standard Molar Chemical Exergy, ech (kJ/kmol), of Selected Substances at 298 K and p0
Substance Formula Model Ia Model IIb
Oxygen O2(g) 3,950 3,970
Carbon dioxide CO2(g) 14,175 19,870
Water H2O(l) 45 900
Hydrogen H2(g) 235,250 236,100
Methane CH4(g) 824,350 831,650
Octane C8H18(l) – 5,413,100
Ethanol C2H5OH(l) 1,342,085 1,357,700
 Example

What is the HHV of methane at T0 = 298.15 K (25oC),

p0 = 1 atm?

=831,680kJ/kmol=51980kJ/kg

Substance Model for HHV LHV ech

Liquid octane Gasoline 47,900 44,430 47,390
Liquid ethanol Biofuel gasoline substitute a
29,670 26,800 29,470b
Gaseous methane Natural gas 55,510 50,020 51,850
a. In the U.S. today ethanol is made from the starch of corn kernels. In Brazil, which is also a
major ethanol producer, sugar cane is used.
b. On a mass basis, the chemical exergy of ethanol is about 2/3 of that for gasoline, thereby
giving lower vehicle fuel mileage when using a blend such as E85 (85% ethanol, 15% gasoline).
 Standard Chemical Exergy

• The chemical exergy of hydrocarbon fuels are

approximated by …
 Standard Chemical Exergy

• The chemical exergy of hydrocarbon fuels are

approximated by their fuel heating values.
 n h  n h
R
i i
P
e e

Substance Model for HHV LHV ech

Liquid octane Gasoline 47,900 44,430 47,390
Liquid ethanol Biofuel gasoline substitute a
29,670 26,800 29,470b
Gaseous methane Natural gas 55,510 50,020 51,850
a. In the U.S. today ethanol is made from the starch of corn kernels. In Brazil, which is also a
major ethanol producer, sugar cane is used.
b. On a mass basis, the chemical exergy of ethanol is about 2/3 of that for gasoline, thereby
giving lower vehicle fuel mileage when using a blend such as E85 (85% ethanol, 15% gasoline).
 Standard Chemical Exergy

• “The chemical exergy of a substance is the maximum

work that can be obtained from it by taking it to
chemical equilibrium with the reference environment
at constant temperature and pressure.” (Rivero &
Garfias, 2006)
• The standard chemical exergy is chemical exergy at
T= 298.15 K and P=1 atm
• For any substance the chemical exergy can be
estimated using:
 Total Exergy

• Total exergy is:

– First evaluate thermomechanical exergy (the system goes
from T, P to T0, P0) and then evaluate the chemical exergy (at
constant T0, P0 the system goes to the reference chemical
composition of the environment)
 Example

Steam at 5 bar, 240ºC leaks from a line in a vapor power

plant. Evaluate the flow exergy of the steam, in kJ/kg,
relative to an environment at T=25ºC, P=1 atm in which
the mole fraction of water vapor is yeH2O=0.0303
 Example

Steam at 5 bar, 240ºC leaks from a line in a vapor power

plant. Evaluate the flow exergy of the steam, in kJ/kg,
relative to an environment at T=25ºC, P=1 atm in which
the mole fraction of water vapor is yeH2O=0.0303

Steam Liquid Water Vapour

5 bar 1 bar 0.0303 bar
240ºC 25ºC 25ºC
 Example

Steam at 5 bar, 240ºC leaks from a line in a vapor power

plant. Evaluate the flow exergy of the steam, in kJ/kg,
relative to an environment at T=25ºC, P=1 atm in which
the mole fraction of water vapor is yeH2O=0.0303
 Example

Methane gas enters a reactor and burns completely with

140% theoretical air. Combustion products exit as a
mixture at temperature T and a pressure of 1 atm. For T
480 and 1560 K, evaluate the flow exergy of the
combustion products, in kJ per kmol of fuel.
 Example

Methane gas enters a reactor and burns completely with

140% theoretical air. Combustion products exit as a
mixture at temperature T and a pressure of 1 atm. For T
480 and 1560 K, evaluate the flow exergy of the
combustion products, in kJ per kmol of fuel.

Combustion Combustion Combustion

Products Products Products at
yP yP yeP
480K 25ºC 25ºC
Exergetic efficiency of an internal combustion engine

• Liquid octane enters an internal combustion engine

operating at steady state with a mass flow rate of
1.810-3 kg/s and is mixed with the theoretical amount
of air. Determine the exergetic efficiency.
 Fuel Cells

• Fuel (H2) and oxidizer (O2)

• 40 a 60 % efficiency
 Example

• Compute the standard chemical exergy of hydrogen,

H2, when T0 = 298.15 K (25oC), p0 = 1 atm.
 Example

• Compute the standard chemical exergy of hydrogen,

H2, when T0 = 298.15 K (25oC), p0 = 1 atm.

H2 + 0.5O2 → H2O(l)

 
eFch  gF  0.5gO2  gH2O(l) (T0, p0 )  eH
ch
2O(l)  0.5 e ch
O2
 Standard Chemical Exergy

gf,oH 2  0 kJ/kmol gf,oO2  0 kJ/kmol

gf,oH 2O  237,180 kJ/kmol

Thermochemical Properties of Selected Substances at 298K and 1 atm TABLE A-25
Heating Values
Enthalpy of Gibbs Function Absolute
Formation, of Formation, Entropy,
Higher, Lower,
Molar Mass, hfo g fo so HHV LHV
Substance Formula M (kg/kmol) (kJ/kmol) (kJ/kmol) (kJ/kmol∙K) (kJ/kg) (kJ/kg)
Carbon C(s) 12.01 0 0 5.74 32,770 32,770
Hydrogen H2(g) 2.016 0 0 130.57 141,780 119,950
Nitrogen N2(g) 28.01 0 0 191.50 – –
Oxygen O2(g) 32.00 0 0 205.03 – –
Carbon Monoxide CO(g) 28.01 –110,530 –137,150 197.54 – –
Carbon dioxide CO2(g) 44.01 –393,520 –394,380 213.69 – –
Water H2O(g) 18.02 –241,820 –228,590 188.72 – –
Water H2O(l) 18.02 –285,830 –237,180 69.95 – –
Hydrogen peroxide H2O2(g) 34.02 –136,310 –105,600 232.63 – –
Ammonia NH3(g) 17.03 –46,190 –16,590 192.33 – –
 Standard Chemical Exergy

ch
eO 2
 3,970 kJ/kmol

2O  900 kJ/kmol
ch
eH
TABLE A-26
Standard Molar Chemical Exergy, ech (kJ/kmol), of Selected Substances at 298 K and p0
Substance Formula Model Ia Model IIb
Oxygen O2(g) 3,950 3,970
Carbon dioxide CO2(g) 14,175 19,870
Water H2O(l) 45 900
Hydrogen H2(g) 235,250 236,100
Methane CH4(g) 824,350 831,650
Octane C8H18(l) – 5,413,100
Ethanol C2H5OH(l) 1,342,085 1,357,700
 Standard Chemical Exergy

ch
eH  
2  0  0.5(0)  (237,180)  (900)  0.5(3,970)

2  236,100 kJ/kmol
ch
eH
TABLE A-26

Standard Molar Chemical Exergy, ech (kJ/kmol), of Selected Substances at 298 K and p0
Substance Formula Model Ia Model IIb
Oxygen O2(g) 3,950 3,970
Carbon dioxide CO2(g) 14,175 19,870
Water H2O(l) 45 900
Hydrogen H2(g) 235,250 236,100
Methane CH4(g) 824,350 831,650
Octane C8H18(l) – 5,413,100
Ethanol C2H5OH(l) 1,342,085 1,357,700