Chapter 3
Chapter 3
Reaction Thermodynamics
Dr. Dawit G
1
Topic
Chemical Reaction
Fuels and Combustion
Theoretical and Actual Combustion Processes
Enthalpy of Formation and Enthalpy of Combustion
Thermodynamic Analysis
First-Law Analysis of Reacting Systems
Adiabatic Flame Temperature
Entropy Change of reacting Systems
Second-Law Analysis of Reacting Systems
2
Chemical Reactions
• We need to consider the chemical internal energy
(which is the energy associated with the destruction
and formation of chemical bonds between the
atoms) when dealing with reacting systems.
3
Fuels and Combustion
Most liquid hydrocarbon fuels (CnHm) are obtained from
crude oil distillation.
Reaction
chamber
For example,
Combustion
chamber
AF =17
7
Example-3.1
One kmol of octane (C8H18) is burned with air that
contains 20 kmol of O2. Assuming the products contain
only CO2, H2O, O2, and N2, determine the mole number of
each gas in the product and the air-fuel ratio for this
combustion process.
Solution :
C8 H18 20O2 3.76 N 2 xCO2 yH 2O zO2 wN 2
x, y, z, and w are determined by applying the mass balance
to each of the elments,
x 8, y 9, z 7.5, and w 75.2 , then,
mair nM air 20 4.76 29 kg air
AF 24.2
m fuel nM C nM H 2 8 12 9 2 kg fuel
8
Completion of the Combustion Process
• The combustion process is complete if all the combustible
components in the fuel are burned to completion. That is, a
combustion process is complete if all the carbon in the fuel
burns to CO2, all the hydrogen burns to H2O , and all the
sulfur (if any) burns to SO2.
• Insufficient oxygen causes incomplete combustion,
unburned fuel, C, H2, CO, or OH would be in the products.
• At ordinary combustion temperatures, nitrogen behaves as
an inert gas and does not react with other chemical
elements.
Combustion
chamber
9
Theoretical and Actual Combustion
• The complete combustion process with no free
oxygen in the products is called stoichiometric, or
theoretical combustion. For example, the theoretical
combustion of methane is
Excess Air
• The air in excess of the stoichiometric amount is
called the excess air. The amount of excess air is
usually expressed in terms of the stoichiometric air as
percent excess air or percent theoretical air.
Example -3.2
Ethane (C2H6) is burned with 20 percent excess air
during a combustion process. Assuming complete
combustion and a total pressure of 100 kPa, determine
the air-fuel ratio for this combustion process.
Solution :
C2 H 6 1.2ath O2 3.76 N 2 2CO2 3H 2O 0.2athO2 1.2 3.76ath N 2
where ath is the stoichiometric coefficient for air.
The coefficient ath is determined from the O2 balance to be
O2 : 1.2ath 2 1.5 0.2ath ath 3.5, then
C2 H 6 4.2O2 3.76 N 2 2CO2 3H 2O 0.7O2 15.79 N 2
mair nM air 4.2 4.76 29 kg air
AF 19.3
m fuel nM C nM H 2 2 12 3 2 kg fuel
12
Example -3.3
A certain natural gas has the following volumetric
analysis: 72% CH4, 9% H2, 14% N2, 2% O2, and 3% CO2.
This gas is now burned with the stoichiometric amount of
air that enters the combustion chamber at 20oC, 1 atm,
and 80% relative humidity. Assuming complete
combustion and a total pressure of 1 atm, determine the
dew-point temperature of the products. (What will be the
answer if the given was as mass analaysis?
Solution :
Considering 1kmol of fuel,
0.72CH 4 0.09H 2 0.14 N 2 0.02O2 0.03CO2 ath O2 3.76 N 2
xCO2 yH 2O zN 2
The unknown coefficients in the above equation are determined
to be x 0.75, y 1.53,ath 1.465, and z 5.648
13
from mass balances on C, H , O2 , and N 2 , respectively.
Next we determine the amount of moisture that accompanie s 4.76 ath
that is 4.76ath 4.761.465 6.97 kmol of dry air.
The partial pressure of the moisture in the air is
Pv ,air P o 0.802.339 kPa 1.871kPa
sat @ 20 C
nv ,air Pv ,air nv ,air 1.871
Assuming ideal - gas behavior,
ntotal Ptotal nv ,air 6.97 101.325
nv ,air 0.131kmol. By adding this amount of H 2O to both sides of the
equation, we have
0.72CH 4 0.09H 2 0.14 N 2 0.02O2 0.03CO2 1.465O2 3.76 N 2
0.131H 2O 0.75CO2 1.661H 2O 5.648N 2
Pv , prod nv , prod Pv , prod 1.661
Also, Pv , prod 20.88 kPa
Pprod n prod 101.325 8.059
Thus, Tdp Tsat @ 20.88 kPa 60.9o C
14
Forms of Energy
The microscopic form of energy of a substance consists
of sensible, latent, chemical, and nuclear energies.
TABLE A 18–26
Enthalpy of Combustion
The difference between the enthalpy of the products at a
specified state and the enthalpy of the reactants at the same
state for a complete reaction is called the enthalpy of reaction
hR.
For combustion processes, the enthalpy of reaction is usually
referred to as the enthalpy of combustion hc, which represents
the amount of heat released during a steady-flow combustion
process when 1 kmol (or 1 kg) of fuel is burned completely at a
specified temperature and pressure.
21
First-Law Analysis of Reacting Systems
The enthalpy of a chemical compound at a specified state is the sum
of the enthalpy of the compound at 25°C, 1 atm (hf°), and the sensible
enthalpy of the compound relative to 25°C, 1 atm.
Taking heat transfer to the system and work done by the system to be
positive quantities, the conservation of energy relation for chemically
reacting steady-flow systems can be expressed per unit mole of fuel as
Q W N p h fo h h o p
N r h fo h h o
r
Q W N p h fo h h o Pv p
N r h fo h h o Pv
r
23
Example -3.5
Liquid propane (C3H8) enters a combustion chamber at 25oC at a
rate of 0.05 kg/min where it is mixed and burned with 50% percent
excess air that enters the combustion chamber at 7oC. An analysis
of the combustion gasses reveals that all the hydrogen in the fuel
burns to H2O but only 90 percent of the carbon burns to CO2, with
the remaining 10 percent forming CO. If the exit temperature of
the combustion gases is 1500 K, determine (a) the mass flow rate
of air and (b) the rate of heat transfer from the combustion
chamber.
Solution :
Assumptions : 1. Steady operating conditions exist.
2. Air and the combustion gases are ideal gases.
3. Kinetic and potential energies are negligible .
24
C3 H 8 l ath O2 3.76 N 2 3CO2 4 H 2Og 3.76ath N 2
O 2 balance : ath 3 2 5
For actual commbustio n with 50% excess air and 10% of C forming
CO in the products,
C3 H 8 l 7.5O2 3.76 N 2 2.7CO2 0.3CO 4 H 2Og 2.65O2 28.2 N 2
( a ) The air - fuel ratio for this combustion process is
AF
mair
7.5 4.76 kmol 29 kg / kmol
25.53kg air/kg fuel
m fuel 3 kmol 12 kg / kmol 4 kmol 2 kg / kmol
Thus, m air AF m fuel 25.53kg air/kg fuel 0.05 kg fuel/min
1.18 kg air/min
b The heat transfer for this steady - flow combustion process is
Qout N p h fo h h o p
N r h fo h h o
r
25
Substance h of h 280 K h 298 K h 1500 K
(kJ/kmol) (kJ/kmol) (kJ/kmol) (kJ/kmol)
C3H8 (l) -118,910 * * *
O2 0 8150 8682 49,292
N2 0 8141 8669 47,073
H2O (g) -241,820 * 9904 57,999
CO2 -393,520 * 9364 71,078
CO -110,530 * 8669 47,517
1 kmol C 3 H 8 118 ,910 h280 h298
o 7.50 8150 8682
N p h fo h h o p
N r h fo h h o
r
Combustion
chamber
27
Theoretical Adiabatic Flame Temperature
29
( a ). The balanced equation for the combustion process with the
theoretical amount of air is
C8 H18 l 12.5O2 3.76 N 2 8CO2 9 H 2O 47 N 2
The adiabatic flame temperatur e in this case is
N p h fo h h o p N r h fo,r Nh fo C8H18
Substance h of h 298 K (Please refer to the ideal
(kJ/kmol) (kJ/kmol) gas Tables A─18 ~ A─27
C8H18 (l) -249,950 * for enthalpy of N2, O2,
O2 0 8682 CO2, CO, H2, H2O, and
N2 0 8669 enthalpy of formation of
H2O (g) -241,820 9904
fuels)
CO2 -393,520 9364
31
b The balanced equation for the complete combustion process
with 400% theoretical air is
C8 H18 l 50O2 3.76 N 2 8CO2 9 H 2O 37.5O2 188N 2
By following the procedure used in ( a ), the adiabatic flame temperatur e
in this case is determined to be T prod 962 K
32
Entropy Change of Reacting Systems
Qk
S gen S prod S react 0 kJ/K
Tk
34
The third law of thermodynamics
35
Absolute Entropy of an Ideal Gas
kJ
Si T , Pi si T , Po Ru ln
o yi Pm
kmol.K
Po
37
Second-Law Analysis of Reaction Systems
Wrev N r g of g g o N g
r p
o
f g go p
kJ
where, h To s h To s To g o 39
Example 3.7 (adiabatic)
Methane (CH4) gas enters a steady-flow adiabatic
combustion chamber at 25oC and 1 atm. It is burned with
50% excess air that also enters at 25oC and 1 atm.
Assuming complete combustion, determine (a) the
temperature of the products, (b) the entropy generation,
and c) the reversible work and exergy destruction.
Assume that To = 298 K and the products leave the
combustion chamber at 1 atm pressure.
Solution :
Assumptions : 1. Steady - flow combustion process.
2. The combustion chamber is adiabatic.
3. There are no work interactio ns. kE PE 0.
4. Air and the combustion gases are ideal gases.
5. Combustion is complete.
40
( a ). The balanced equation for the complete combustion process
with 50% excess air is
CH 4 g 3O2 3.76 N 2 CO2 2 H 2O O2 11.28 N 2
Under steady - flow conditions, the adiabatic flame temperatur e is
determined from H prod H react , which reduces to
p f
N h o
h h o
p
N r h fo,r Nh fo CH 4
Substance h of h 298 K
(kJ/kmol) (kJ/kmol)
CH4 (g) -74,850 *
O2 0 8682
N2 0 8669
H2O (g) -241,820 9904
CO2 -393,520 9364
43
Example 3.8 (isothermal)
Methane (CH4) gas enters a steady-flow combustion
chamber at 25oC and 1 atm. It is burned with 50% excess
air, which also enters at 25oC and 1 atm. After
combustion, the products are allowed to cool to 25oC.
Assuming complete combustion, determine (a) the heat
transfer per kmol of CH4, (b) the entropy generation, and
c) the reversible work and exergy destruction. Assume
that To = 298 K and the products leave the combustion
chamber at 1 atm pressure.
Solution :
This is the same combustion process as discussed in the previous example,
except that the combustion products are brought to the state of the
surroundin gs by transfering heat from them. Thus the combustion equation
remains the same
CH 4 g 3O2 3.76 N 2 CO2 2 H 2O O2 11.28 N 2
44
At 25o C, part of the water vapor will condense. The amount of water vapor
that remains in the products is determined from
P
Nv v @ 25o C Nv 3.169 kPa
N v 0.43 kmol
N gas Ptotal 13.28 N v 101.325 kPa
Therefore, 1.57 kmol of the H 2O formed will be in the liquid form, which will
be removed at 25 o C and 1 atm.
Substance h of
Heat transfer during this steady - flow (kJ/kmol)
combustion process is determined from CH4 (g) -74,850
the steady - flow energy balance H2O (l) -285,830
Qout N h N h
o
p f p
o
r f r
H2O (g)
CO2
-241,820
-393,520
Thus
Qout 1kmol CH 4 74,850 kJ / kmol CH 4
1kmol CO2 393,520 kJ / kmol CO2
0.43 kmol H 2Og 241,820 kJ / kmol H 2Og
1.57 kmol H 2Ol 285,830 kJ / kmol H 2Ol 871,406 kJ / kmol CH 4
45
(b ). The total entropy generation during this process is determined from
an entropy balance applied on an extended system that includes the
immediate surroundin gs of the combustion chamber
Q
S gen S prod S react out
Tsurr
48