CHPT 14

Chapter 14 Lecture notes for Thermodynamics: An Engineering Approach, 3rd Ed by Cengel and Boles
Chapter 14: CHEMICAL REACTIONS
The combustion process is a chemical reaction where by fuel is oxidized and energy is
released.
CO2
Fuel Combustion
CnHm Chamber H2O
N2
Air
Products
Reactants Qnet PP, TP
TR, PR
Fuels are usually composed of some compound or mixture containing carbon, C, and
hydrogen, H2.
Examples of hydrocarbon fuels are:
CH4 Methane
C8H18 Octane
Coal Mixture of C, H2, S, O2, N2 and non-combustibles
Initially, we shall consider only those reactions that go to completion. The components
prior to the reaction are called Reactants and the components after the reaction are
called
Products
Reactants  Products
For example all carbon is burned to carbon dioxide and all hydrogen is converted into
water.
C  O2  CO2
1
H2  O2  H2 O
2
A complete combustion process is one where all carbon is burned to carbon dioxide
(CO2) and all hydrogen is converted into water (H2O).
Example:
Chapter 14-1
A complete combustion of octane in oxygen is represented by the balanced

combustion equation. The balanced combustion equation is obtained by making sure we
have the same number of atoms of each element on both sides of the equation. That is
we make sure the mass is conserved.
C8 H18  A O2  B CO2  D H2 O
Note we often can balance the C and H for complete combustion by inspection.
C8 H18  A O2  8 CO2  9 H2 O
The amount of oxygen is found from the oxygen balance.
O: A(2)  8(2)  9(1)

A  12.5
C8 H18  12.5 O2  8 CO2  9 H2 O

Note: Mole numbers are not conserved but we have conserved the mass on a total basis
as well as a specie basis.
The complete combustion process is also called the Stoichiometric combustion, and all
coefficients are called the Stoichiometric coefficients.
In most combustion processes oxygen is supplied in the form of air rather than pure
oxygen.
Air is assumed to be 21% oxygen and 79% nitrogen on a volume basis. For ideal gas
mixtures, percent by volume is equal to percent by moles. Thus, for each mole of
oxygen in air, there exists 79/21 = 3.76 moles of nitrogen. Therefore, complete or
theoretical combustion of octane with air can be written as
C8 H18  12.5 ( O2  3. 76 N 2 ) 
8 CO2  9 H2 O  47 N 2
Chapter 14-2
Air-Fuel Ratio
Since the total moles of a mixture is equal to the sum of moles of each component, there
are 12.5(1 + 3.76) = 59.5 moles of air required for each mole of fuel for the complete
combustion process.
Often complete combustion of the fuel will not occur unless there is an excess of air
present greater than just the theoretical air required for complete combustion.
To determine the amount of excess air supplied for a combustion process, let us define
the air-fuel ratio, AF as
kmol air
AF 
kmol fuel
Thus for the above example, the theoretical air fuel ratio is
12.5(1  3.76) kmol air

AFth   59.5
1 kmol fuel
On a mass basis the theoretical air fuel ratio is
kg air
28.97
kmol air kmol air
AFth  59.5
kmol fuel [8(12)  18(1)] kg fuel
kmol fuel
kg air
 1512
.
kg fuel
Chapter 14-3
Percent Theoretical and Percent Excess Air
In most cases more than theoretical air is supplied to insure complete combustion and to
reduce or eliminate carbon monoxide (CO) from the products of combustion. The
amount of excess air is usually expressed as percent theoretical air and percent excess
air.
AFactual
Percent theoretical air  100%
AFth
AFactual  AFth
Percent excess air  100%
AFth
Show that these results may be expressed in terms of the moles of oxygen only as
N O2 actual
N O2 th
N O2 actual  N O2 th
N O2 th
Write the combustion equation of octane with 120% theoretical air (20% excess air)
C8 H18  12
. (12.5) (O2  3.76 N 2 ) 
8 CO2  9 H2 O  (0.2)(12.5) O2  12
. (47) N 2
Note that (1)(12.5)O2 is required for complete combustion to produce 8 kmol of carbon
dioxide and 9 kmol of water; therefore, (0.2)(12.5)O2 is found as excess oxygen in the
products.
Chapter 14-4
C8 H18  12
. (12.5) (O2  3.76 N 2 ) 
8 CO2  9 H2 O  2.5 O2  12
. (47) N 2
Second method to balance the equation for excess air(see text):
C8 H18  12
. Ath (O2  3.76 N 2 ) 
8 CO2  9 H2 O  0.2 Ath O2  12
. (47) N 2
O: . Ath (2)  8(2)  9(1)  0.2 Ath (2)

12
Ath  12.5
Incomplete Combustion With Known % Theoretical Air
Consider combustion of C8H18 with 120 % Th. air where 80 % C in the fuel goes into
CO2
C8 H18  12
. (12.5) (O2  3.76 N 2 ) 
0.8(8) CO2  0.2(8) CO  9 H2 O  X O2  12
. (47) N 2
O balance gives
O: . (12.5)(2)  0.8(8)(2)  0.2(8)(1)  9(1)  X (2)
12
X  3.3
Why is X>2.5?
Then the balanced equation is
Chapter 14-5
C8 H18  12
. (12.5) (O2  3.76 N 2 ) 
6.4 CO2  16
. CO  9 H2 O  3.3 O2  12
. (47) N 2
Combustion Equation When Product Gas Analysis Is Known
Propane gas C3H8 is reacted with air such that the dry product gases are 11.5% CO2,
2.7% O2, and 0.7% CO by volume. What percent theoretical air was supplied? What is
the dew point temperature of the products if the product pressure is 100 kPa?
We assume 100 kmol of dry product gases; then, the percent by volume can interpreted
to be mole numbers. But, we do not know how much fuel and air were supplied or
water formed to get the 100 kmol of dry product gases.
X C3 H8  A (O2  3.76 N 2 ) 
. CO2  0.7 CO  2.7 O2  B H2 O  A(3.76) N 2
115
The unknown coefficients A, B, and X are found by conservation of mass for each
species.
C: X (3)  115
. (1)  0.7(1) X  4.07
H: X (8)  B (2) B  16.28
O: A(2)  115 . (2)  0.7(1)
 2.7(2)  B (1) A  22.69
N 2 : A(3.76)  85.31
The balanced equation is
4.07 C3 H8  22.69 (O2  3.76 N 2 ) 

. CO2  0.7 CO  2.7 O2  16.28 H2 O  85.31 N 2
115
Second method to find A:
Assume the remainder of the 100 kmol of dry product gases is N2.
Chapter 14-6
kmol N 2  100  (115

.  0.7  2.7)  851
.
Then A is
851.
A  22.65 ( fairly good check )
3.76
These two methods don’t give the same results for A; but, they are close.
What would be the units on the coefficients in the balanced combustion equation?
Generally we should write the combustion equation per kmol of fuel. To write the
combustion equation per unit kmol of fuel divide by 4.07:
C3 H8  557
. (O2  3.76 N 2 ) 
2.83 CO2  017
. CO  0.66 O2  4.0 H2 O  20.96 N 2
The actual air-fuel ratio is
kg air
. (1  3.76) kmol air 28.97
557
kmol air
AFth 
kg fuel
1kmol fuel[3(12)  8(1)]
kmol fuel
kg air
 17.45
kg fuel
The theoretical combustion equation is
C3 H8  5 (O2  3.76 N 2 ) 
3 CO2  4.0 H2 O  18.80 N 2
The theoretical air-fuel ratio is
Chapter 14-7
kg air
(5)(1  3.76) kmol air 28.97
kmol air
AFth 
kg fuel
1kmol fuel[3(12)  8(1)]
kmol fuel
kg air
 15.66
kg fuel
The percent theoretical air is
AFactual
AFth
17.45
 100  111%
15.66
or
N O2 actual
N O2 th
557
.
 100  111%
5
The percent excess air is
Chapter 14-8
AFactual  AFth
AFth
17.45  15.66
 100  11%
15.66
Dew Point Temperature:
Dew Point
The dew point temperature for the product gases is the temperature at which the water in
the product gases would begin to condense when the products are cooled at constant
pressure. The dew point temperature is equal to the saturation temperature of the water
at its partial pressure in the products.
TDP  Tsat at Pv  yv Pproducts

N water
yv 
 Ne products
4
yv   01398
.
2.83  017.  0.66  4  20.96
Pv  yv Pproducts  01398
. (100 kPa )
 13.98 kPa
TDP  Tsat at13.98 kPa
= 52.44 o C
Chapter 14-9
What would happen if the product gases are cooled to 100oC or to 30oC?
Example
An unknown hydrocarbon fuel, CXHY is reacted with air such that the dry product gases
are 12.1% CO2, 3.8% O2, and 0.9% CO by volume. What is the average make-up of the
fuel?
We assume 100 kmol (Do you have to always assume 100 kmol?) of dry product gases;
then the percent by volume can interperted to be mole numbers. We do not know how
much air was supplied or water formed to get the 100 kmol of dry product gases. But,
we assume 1 kmol of unknown fuel.
C X HY  A (O2  3.76 N 2 ) 
12.1 CO2  0.9 CO  38. O2  B H2 O  D N 2
The 5 unknown coefficients A, B, D, X, and Y are found by conservation of mass for
each species, C, H, O, and N plus one other equation. Here we use the subtraction
method for the nitrogen to generate the fifth independent equation for the unknowns.
X C3 H8  A (O2  3.76 N 2 ) 
. CO2  0.7 CO  2.7 O2  B H2 O  A(3.76) N 2
115
The unknown coefficients A, B, and X are found by conservation of mass for each
species.
N 2 : D  100  (12.1  0.9  38
. )  83.2
D 83.2
O2 : A    22.13
3.76 3.76
O: A(2)  (12.1)(2)  (0.9)(1)  (38
. )(2)  B (1)
B  1154
.
C: 1( X )  12.1(1)  (0.9)(1)
X  13.0
H: 1(Y )  B (2)
Y  23.08
Chapter 14-10
The balanced equation is
C13 H23.08  22.13 (O2  3.76 N 2 ) 

12.1 CO2  0.9 CO  38 . O2  1154. H2 O  83.2 N 2
Enthalpy of Formation
When a compound is formed from its elements ( e.g. Methane, CH4, from C and H2),
heat transfer occurs. When heat is given off, the reaction is called exothermic. When
heat is required, the reaction is called endothermic. Consider the following
Methane
C Reaction Chamber
CH4
(Back Yard Compost Pile)
2H2
Reactants Products
TR = 298 K Qnet TP = 298 K
PR = 1 Atm PP = 1 Atm
C  2 H2  CH4
The conservation of energy for a steady-flow combustion process is
Ein  E out
Qnet  HReactants  HProducts
Qnet  HProducts  HReactants
Chapter 14-11
Qnet  N h
Products
e e  Nh
Reactants
i i
Qnet  1hCH4  (1hC  1hH2 )
We need to establish a common reference state for the enthalpies of reacting

components.
The enthalpy of the elements or their stable compounds is

defined to be ZERO at 25oC (298 K) and 1 atm (or 0.1
MPa).
Qnet  1hCH4  (1(0)  1(0))

 hCH4
This heat transfer is called the enthalpy of formation for methane, h fo . The superscript
(o) implies the 1 atm pressure value and the subscript (f) implies 25oC data. h fo is given
in Table A.26.
During the formation of methane from the elements at 298 K, 0.1 MPa, heat is given off
(an exothermic reaction) such that
kJ
Qnet  h fo CH  74,850
4 kmolCH4
The enthalpy of formation, h fo , is tabulated for typical compounds. The enthalpy of

formation of the elements in their stable form is taken as zero. The enthalpy of
formation of the elements found naturally as diatomic elements, such as nitrogen,
oxygen, and hydrogen, is defined to be zero. The enthalpies of formation and specific
heats for several combustion components is given in the following table
Chapter 14-12
Substance Formula M h fo
kJ/kmol
Air 29 0
Oxygen O2 32 0
Nitrogen N2 28 0
Carbon Dioxide CO2 44 -393,520
Carbon Monoxide CO 28 -110,530
Water (vapor) H2Ovap 18 -241,820
Water (liquid) H2Oliq 18 -285,830
Methane CH4 16 -74,850
Acetylene C2H2 26 +226,730
Ethane C2H6 30 -84,680
Propane C3H8 44 -103,850
Butane C4H10 58 -126,150
Octane (vapor) C8H18 114 -208,450
Dodecane C12H26 170 -291,010
The enthalpies are calculated relative to a common base or reference called the enthalpy
of formation. The enthalpy of formation is the heat transfer required to form the
compound from its elements at 25oC (77 °F) or 298 K (537 R), 1 atm. The enthalpy at
any other temperature is given as
h  h fo  (hT  h o )
Here the term h o is the enthalpy of any component at 298 K. The enthalpies at the
temperatures T and 298 K can be found in Tables A-18 through A-25. If tables are not
available, the enthalpy difference due to the temperature difference can be calculated
from
(hT  h o )  CP (T  298)
Chapter 14-13
When the reactants and products are at temperatures other than 298 K, the enthalpy is
given by
The heat transfer is
Qnet  H P  H R
  N [h
Products
e f
o
 (hT  h o )]e   N [h
Reactants
i f
o
 (hT  h o )]i
Example:
Butane gas C4H10 is burned in theoretical air as shown below. Find the net heat transfer
per kmol of fuel.
CO2
Fuel Combustion
H2O
C4H10 Chamber
N2
Theoretical
Air
Products
Reactants Qnet PP, TP
TR, PR
Balanced combustion equation:
C4 H10  6.5 (O2  3.76 N 2 ) 

4 CO2  5 H2 O  24.44 N 2
The steady-flow heat transfer is
  N [h
Products
e f
o
 (hT  h o )]e   N [h
Reactants
i f
o
 (hT  h o )]i
Chapter 14-14
Reactants: TR = 298 K
Comp Ni h fo hT ho N i [h fo  (hT  h o )]
kmol/kmol fuel kJ/kmol kJ/kmol
kJ/kmol kJ/kmol fuel
C4H10 1 -126,150 - - -126,150
O2 6.5 0 8,682 8,682 0
N2 24.44 0 8,669 8,669 0
HR   N [h
Reactants
i f
o
 (hT  h o )]i
kJ
 126,150
kmol C4 H10
Products: TP = 1000 K
Comp Ne h fo hT ho N e [h fo  (hT  h o )]
kmol/kmol fuel kJ/kmol kJ/kmol
kJ/kmol kJ/kmol fuel
CO2 4 -393,520 42,769 9,364 -1,440,460
H2O 5 -241,820 35,882 9,904 -1,079,210
N2 24.44 0 30,129 8,669 +524,482
HP   N [h
Products
e f
o
 (hT  h o )]e
kJ
 1,995,188
kmol C4 H10
Chapter 14-15
kJ
 1,869,038
kmol C4 H10
Adiabatic Flame Temperature
The temperature the products have when a combustion process takes place
adiabatically is called the adiabatic flame temperature.
Example:
Liquid octane, C8H18(liq) is burned with 400 % theoretical air. Find the adiabatic flame
temperature when the reactants enter at 298 K, 0.1 MPa and the products leave at
0.1MPa.
CO2
Fuel Combustion O2
C8H18 Chamber
H2O
400% N2
Th Air
Products
Reactants TP = ?
Qnet = 0
TR = 298 K PP = 0.1MPa
PR = 0.1 MPa
The combustion equation is
C8 H18  4(12.5) (O2  3.76 N 2 ) 

8 CO2  37.5 O2  9 H2 O  188 N 2
Chapter 14-16
  N [h
Products
e f
o
 (hT  h o )]e   N [h
Reactants
i f
o
 (hT  h o )]i
 0 ( Adiabatic Combustion)
Thus, HP = HR for adiabatic combustion. We need to solve this equation for TP.
Since the reactants are at 298 K, ( hT  h o )i = 0,
HR  Nh
Reactants
i
o
f i
 1( 249,950)  4(12.5)(0)  4(12.5)(3.76)(0)

kJ
 249,950
kmol C4 H10
Since the products are at the adiabatic flame temperature, TP 298 K,
HP   N [h
Products
e f
o
 (hTP  h o )]e
 8( 393,520  hTP  9364) CO2

 9( 241,820  hTP  9904) H2 O
 37.5(0  hTP  8682) O2
 188(0  hTP  8669) N 2
H P  ( 7,443,845  8hTP , CO2  9hTP , H2 O

kJ
 37.5hTP , O2  188hTP , N 2 )
kmol C4 H10
Thus, setting HP = HR yields
Chapter 14-17
8hTP , CO2  9hTP , H2 O  37.5hTP , O2  188hTP , N 2  7,193,895

To estimate TP, assume all products behave like N2 and estimate the adiabatic flame
temperature from the nitrogen data, Table A-18.
242.5hTP , N 2  7,193,895
kJ
hTP , N 2  29,6655
.
kmol N 2
Tp  985 K
Because of the tri-atomic CO2 and H2O, the actual temperature will be somewhat less
than 985 K. Try 960 K and 970K.
Ne h960 K h970 K
CO2 8 40,607 41,145
H2O 9 34,274 34,653
O2 37.5 29,991 30,345
N2 188 28,826 29,151
N h e TP , e
7,177,572 7,259,362
Produts
Interpolation gives: TP = 962 K
Example
Liquid octane, C8H18(liq) is burned with excess air. The adiabatic flame temperature is
960 K when the reactants enter at 298 K, 0.1 MPa and the products leave at 0.1MPa.
What percent excess air is supplied?
CO2
Fuel Combustion O2
C8H18(liq) Chamber
H2O
Excess N2
Air
Products
Reactants TP = 960 K
Qnet = 0
TR = 298 K PP = 0.1MPa
PR = 0.1 MPa
Chapter 14-18
Let A be the excess air; then combustion equation is
C8 H18  (1  A)(12.5) (O2  3.76 N 2 ) 

8 CO2  12.5 A O2  9 H2 O  (1  A)(12.5)(3.76) N 2
  N [h
Products
e f
o
 (hT  h o )]e   N [h
Reactants
i f
o
 (hT  h o )]i
Here, since the temperatures are known, the hTP are known. The product gas mole
numbers are unknown but are functions of the amount of excess air, A. The energy
balance can be solved for A.
A3
Thus 300% excess, or 400% theoretical, air is supplied.
Example
Tabulate the adiabatic flame temperature as a function of excess air for the complete
combustion of C3H8 when the fuel enters the SSSF reaction chamber at 298 K and the air
enters at 400 K.
The combustion equation is:
C3 H8  (1  A)(5) (O2  3.76 N 2 ) 

3 CO2  5 A O2  4 H2 O  (1  A)(5)(3.76) N 2
Where A is the value of excess air in decimal form.
Chapter 14-19
  N [h
Products
e f
o
 (hT  h o )]e   N [h
Reactants
i f
o
 (hT  h o )]i
% Excess Air Adiabatic Flame Temp. K

0 2459.3
20 2191.9
50 1902.5
100 1587.1
217 1200
Enthalpy of Reaction and Enthalpy of Combustion
When the products and reactants are at the same temperature, the enthalpy of reaction
hR, is the difference in their enthalpies. When the combustion is assumed to be complete
with theoretical air supplied the enthalpy of reaction is called the enthalpy of
combustion, hC. The enthalpy of combustion can be calculated any value of the
temperature but it is usually determined at 25oC or 298 K. See Table A.27 for the
enthalpy of combustion at 25oC.
hC  H P  H R when TP  TR  25o C  298 K

 N h
Products
e
o
f e  Nh
Reactants
i
o
f i
Chapter 14-20
Heating Value
The heating value, HV, of a fuel is the absolute value of the enthalpy of combustion or
just the negative of the enthalpy of combustion.
HV  hC
The lower heating value, LHV, is the heating value when water appears as a gas in the
products.
LHV  hC   hC with H2 Ogas in products

The lower heating value is often used as the amount of energy per kmol of fuel supplied
to the gas turbine engine.
The higher heating value, HHV, is the heating value when water appears as a liquid in
the products.
HHV  hC   hC with H2 Oliquid in products

The higher heating value is often used as the amount of energy per kmol of fuel supplied
to the steam power cycle.
The higher and lower heat values are related by the amount of water formed during the
combustion process and the enthalpy of vaporization of water at the temperature.
HHV  LHV  N H2O h fg H2 O
Chapter 14-21
Example
The enthalpy of combustion of gaseous C8H18 at 25oC with liquid water in the products is
-5,512,200 kJ/kmol (see Table A-27). Find the lower heating value of liquid octane.
LHVC8 H18 gas  HHVC8 H18 gas  N H2 O h fg H2 O

kJ kmol H2 O kJ
 5,512,200 9 (44,010)
kmol C8 H18 kmol C8 H18 kmol H2 O
kJ
 5,116,110
kmol C8 H18
LHVC8 H18 liq  LHVC8 H18 gas  h fg C8 H18

kJ
 (5,116,110  41,460)
kmol C8 H18
kJ
 5,074,650
kmol C8 H18 liq
Can you explain why LHVliq < LHVgas?
Closed System Analysis:
Example:
A mixture of 1 kmol C8H18 gas and 200% excess air at 25oC, 1 atm is burned completely
in a closed system (a bomb) and is cooled to 1200 K. Find the heat transfer from the
system and the system final pressure.
1 kmol C8H18 gas Wnet

200% Excess Air
T1 = 25oC
Qnet P1 = 1 Atm Rigid
T2 = 1200 K Container
Chapter 14-22
Apply First Law Closed System:
Ein  Eout  E
Qnet  Wnet  U P  U R
Wnet  0 ( Rigid Container )
Qnet  U P  U R  H P  ( PV ) P  H R  ( PV ) R b g
b
 H P  H R  ( PV ) P  ( PV ) R g
Assume that the reactants and products are ideal gases, then
PV  NRu T
Qnet  H P  H R 
L
M N e Ru Te  N R TP
O
N Products Reactants
i u i
Q
  N [h
Products
e f
o
 (hT  h o )  Ru T ]e
  N [h
Reactants
i f
o
 (hT  h o )  Ru T ]i
The balanced combustion equation for 200% excess (300% theoretical) air is
C8 H18  (3)(12.5) ( O2  3.76 N 2 ) 

8 CO2  25 O2  9 H2 O  141 N 2
Chapter 14-23
Qnet  8( 393,520  53,848  9,364  8.314(1200)) CO2

 9( 241,820  44,380  9,904  8.314(1200)) H2 O
 25(0  38,447  8,682  8.314(1200)) O2
 141(0  36,777  8,669  8.314(1200)) N 2
 1( 208,450  h298 K  h o  8.314(1200)) C8 H18
 25(0  8,682  8,682  8.314(1200)) O2
 141(0  8,669  8,669  8.314(1200)) N 2
kJ
 112
.  106
kmol C8 H18
To find the final pressure, we assume that the reactants and products are ideal gas
mixtures.
1 1  N 1 Ru T1
PV
2 2  N 2 Ru T2
PV
Where state 1 is the state of the mixture of reactants before the combustion process and
state 2 is the state of the mixture of products after the combustion process takes place.
Note that the total moles of reactants are not equal to the total moles of products.
PV N 2 Ru T2
2 2

PV
1 1 N 1 Ru T1
But, V2 = V1.
Chapter 14-24
N 2 T2
P2  P1
N1 T1
F
 1 AtmG
183 kmol Products IF
JG1200 K I
J
H
179.5 kmol Reactants KH K
298 K
 4.11 Atm
Second Law Analysis of Reacting Systems
Second Law for the Open System
Mass Reservoir, Ni Ne Mass Reservoir,

component i component e
Reacting
Ti Te
System
Pi Pe
Qk
Surroundings
Tk
The entropy balance relations developed in Chap. 6 are equally applicable to both
reacting and non-reacting systems provided that the entropies of individual constituents
are evaluated properly using a common basis.
Taking the positive direction of heat transfer to be to the system, the entropy balance
relation can be expressed for a steady-flow combustion chamber as
Qk
 T  S gen  SProd  SReact  0 ( kJ / k )
k
For an adiabatic process the entropy balance relation reduces to
S gen , adiabatic  SProd  S React  0

The third law of thermodynamics states that the entropy of a pure crystalline substance at
absolute zero temperature is zero. The third law provides a common base for the entropy
Chapter 14-25
of all substances, and the entropy values relative to this base are called the absolute
entropy.
The ideal-gas tables list the absolute entropy values over a wide range of temperatures
but at a fixed pressure of Po = 1 atm. Absolute entropy values at other pressures P for any
temperature T are determined from
P
s ( T , P )  s o (T , Po )  Ru ln [ kJ / ( kmol  K )]
Po
For component i of an ideal-gas mixture, the absolute entropy can be written as
yi Pm
si (T , Pi )  sio ( T , Po )  Ru ln [ kJ / ( kmol  K )]
Po
where Pi is the partial pressure, yi is the mole fraction of the component, and Pm is
the total pressure of the mixture in atmospheres.
Example:
A mixture of ethane gas, C2H6, and oxygen enters a combustion chamber at 1 atm, 25oC.
The products leave at 1 atm, 900 K. Assuming complete combustion, does the process
violate the second law?
C2H6 CO2
Reacting
O2 System H2O
TR = 25oC
PR = 1 Atm TP = 900 K
Qsurr PP = 1 Atm
Surroundings
Tsurr = 25oC
The balanced combustion equation is:
C2 H6  35
. O2  2 CO2  3 H2 O
The mole fractions for the reactants and products are
Chapter 14-26
1 1
yC2 H6  
1  35
. 4.5
35
. 35
.
yO2  
1  35
. 4.5
2 2
yCO2  
23 5
3 3
y H2 O  
23 5
Now to calculate the individual component entropies.
For the reactant gases:
yC2 H6 Pm
sC2 H6 (T , PC2 H6 )  sCo2 H6 (T , Po )  Ru ln
Po
L
M F 1 I O
P
229.49  8.314 lnG J
1 Atm
M P kJ
M G
G 1 Atm J
4.5
J Pkmol K
N H KQ C2 H6
kJ
 242.0
kmolC2 H6  K
yO2 Pm
sO2 ( T , PO2 )  sOo2 ( T , Po )  Ru ln
Po
L
M F35
. I O
P
205.03  8.314 lnG J
1 Atm
M P kJ
M G
G 1 Atm J
4.5
J Pkmol  K
N H KQ O2
kJ
 207.1
kmolO2  K
Chapter 14-27
S React  N s
Reactants
i i
 1(242.0)  35
. (207.1)
kJ
 966.9
kmolC2 H6  K
For the product gases:
yCO2 Pm
sCO2 (T , PCO2 )  sCO
o
( T , Po )  Ru ln
2
Po
L
M F2 I O
P
263.56  8.314 lnG J
1 Atm
M P kJ
M G
G
5
1 Atm J
J Pkmol K
N H KQ CO2
kJ
 2712
.
kmolCO2  K
y H2 O Pm
sH2 O (T , PH2 O )  sHo2 O (T , Po )  Ru ln
Po
L
M F3 I O
P
228.32  8.314 lnG J
1 Atm
M P kJ
M G
G1 Atm J
5
J Pkmol K
N H KQ H2 O
kJ
 232.6
kmolH2 O  K
Chapter 14-28
S Prod  N s
Products
e e
 2(2712
. )  3(232.6)
kJ
 1240.2
kmolC2 H6  K
The entropy change for the combustion process is
kJ
S Prod  S React  (1240.2  966.9)
kmolC2 H6  K
kJ
 273.3
kmolC2 H6  K
Now to find the entropy change due to heat transfer with the surroundings. The steady-
flow conservation of energy for the control volume is
Qnet sys  H P  H R
  N [h
Products
e f
o
 (hT  h o )]e   N [h
Reactants
i f
o
 (hT  h o )]i
Qnet sys  2( 393,520  37,405  9,364) CO2

 3( 241,820  31,828  9,904) H2 O
 1( 214,820  h298 K  h o ) C2 H6
 35
. (0  8,682  8,682) O2
kJ
 1306
.  106
kmol C2 H6
Chapter 14-29
Qk Qnet sys
T  T
k o
kJ
1306
.  106
kmol C2 H6

(25  273) K
kJ
 4,383
kmol C2 H6  K
The entropy generated by this combustion process is
Qk
S gen  S Prod  SReact   0
Tk
b
 273.3  ( 4383)
kJ
g
kmol C2 H6  K
kJ
 4656.3
kmol C2 H6  K
Since Sgen, or Snet , is  0, the second law is not violated.
Chapter 14-30

CHPT 14

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Chapter 14 Lecture notes for Thermodynamics: An Engineering Approach, 3rd Ed by Cengel and Boles

Chapter 14: CHEMICAL REACTIONS

Examples of hydrocarbon fuels are:

A complete combustion of octane in oxygen is represented by the balanced

O: A(2)  8(2)  9(1)

C8 H18  12.5 O2  8 CO2  9 H2 O

12.5(1  3.76) kmol air

Percent Theoretical and Percent Excess Air

Second method to balance the equation for excess air(see text):

O: . Ath (2)  8(2)  9(1)  0.2 Ath (2)

Incomplete Combustion With Known % Theoretical Air

Then the balanced equation is

Combustion Equation When Product Gas Analysis Is Known

4.07 C3 H8  22.69 (O2  3.76 N 2 ) 

kmol N 2  100  (115

TDP  Tsat at Pv  yv Pproducts

The balanced equation is

C13 H23.08  22.13 (O2  3.76 N 2 ) 

The conservation of energy for a steady-flow combustion process is

Qnet  HProducts  HReactants

Qnet  1hCH4  (1hC  1hH2 )

We need to establish a common reference state for the enthalpies of reacting

The enthalpy of the elements or their stable compounds is

Qnet  1hCH4  (1(0)  1(0))

The enthalpy of formation, h fo , is tabulated for typical compounds. The enthalpy of

The heat transfer is

Balanced combustion equation:

C4 H10  6.5 (O2  3.76 N 2 ) 

Adiabatic Flame Temperature

The combustion equation is

C8 H18  4(12.5) (O2  3.76 N 2 ) 

The steady-flow heat transfer is

Since the reactants are at 298 K, ( hT  h o )i = 0,

 1( 249,950)  4(12.5)(0)  4(12.5)(3.76)(0)

 8( 393,520  hTP  9364) CO2

H P  ( 7,443,845  8hTP , CO2  9hTP , H2 O

8hTP , CO2  9hTP , H2 O  37.5hTP , O2  188hTP , N 2  7,193,895

Interpolation gives: TP = 962 K

Let A be the excess air; then combustion equation is

C8 H18  (1  A)(12.5) (O2  3.76 N 2 ) 

The steady-flow heat transfer is

The combustion equation is:

C3 H8  (1  A)(5) (O2  3.76 N 2 ) 

The steady-flow heat transfer is

% Excess Air Adiabatic Flame Temp. K

Enthalpy of Reaction and Enthalpy of Combustion

hC  H P  H R when TP  TR  25o C  298 K

LHV  hC   hC with H2 Ogas in products

HHV  hC   hC with H2 Oliquid in products

HHV  LHV  N H2O h fg H2 O

LHVC8 H18 gas  HHVC8 H18 gas  N H2 O h fg H2 O

LHVC8 H18 liq  LHVC8 H18 gas  h fg C8 H18

Closed System Analysis:

1 kmol C8H18 gas Wnet

Apply First Law Closed System:

C8 H18  (3)(12.5) ( O2  3.76 N 2 ) 

Qnet  8( 393,520  53,848  9,364  8.314(1200)) CO2

Second Law Analysis of Reacting Systems

Second Law for the Open System

Mass Reservoir, Ni Ne Mass Reservoir,

For an adiabatic process the entropy balance relation reduces to

S gen , adiabatic  SProd  S React  0

The balanced combustion equation is: