Chapter 13

Reacting Mixtures and

Combustion
Photo courtesy of www.freefoto.com
Fundamentals
products fuel oxidizer + reactants products
Chemical Equations:
2 2 2
1
1H O 1H O
2
+
2 2 2
1
1 kmol H kmol O 1 kmol H O
2
+
2 2 2
2 kg H 16 kg O 18 kg H O +
Modeling Air:
79% Nitrogen, 21% Oxygen
Only the Oxygen reacts: Nitrogen considered inert
M
air
= 28.97 kg/kmol or lb/lbmol (Tables A-1)
Air Fuel Ratio:
mass of air moles of air
mass of fuel moles of fuel
air air
fuel fuel
M M
AF AF
M M
| |

= =
|
|

\ .
1 a
2 b
1 * b 2 * a
2 * b 2 * 1
O H * b O * a H * 1
2 2 2
=
=
=
=
= +
Fundamentals
Chemical Equations:
Common fuels modeled as simple hydrocarbons:
Natural Gas Methane (CH
4
)
Gasoline Octane (C
8
H
18
)
Diesel Dodecane (C
12
H
26
)
Theoretical Air:
The minimum amount of air that provides the necessary oxygen
for complete combustion (i.e. For one mole of octane the
theoretical air is 59.5 moles)
2 * d 2 * 0.79 * a N)
1 * c 2 * b 2 * 0.21 * a O)
2 * c 18 * 1 H)
1 * b 8 * 1 C)
=
+ =
=
=
47.0 d
59.5 a
9 c
8 b
=
=
=
=
2 2 2 2 2 18 8
N * d O H * c CO * b ) 0.21N (0.21O * a H C * 1 + + = + +
Stoichiometric Coefficients (Four equations and four unknowns)
Fundamentals
2 * d 2 * 0.79 * 59.5 * 1.5 N)
2 * e 1 * 9 2 * 8 2 * 0.21 * 59.5 * 1.5 O)
=
+ + =
25 . 6 e
70.5 d
=
=
2 2 2 2 2 2 18 8
O * e N * d O H * 9 CO * 8 ) 0.79N (0.21O * 59.5 * 5 . 1 H C * 1 + + + = + +
Stoichiometric Coefficients (Two equations and two unknowns)
Percent Excess Air:
The percent of air supplied that is in excess of the theoretical air
Example: Combustion of Octane with 50% excess air (or 150% theoretical)
2 2 2 2 2 2 18 8
O * 25 . 6 N * 70.5 O H * 9 CO * 8 ) 0.79N (0.21O * 25 . 89 H C * 1 + + + = + +
Quiz
One kg/min of methane is burned in a combustor with 25% excess air.
The temperature and pressure of the air and fuel are 25
o
C and 101kPa
respectively. The design velocity for each intake is 15 m/s. Determine the
diameter of the air intake line in meters.
Quiz
One kg/min of methane is burned in a combustor with 25% excess air.
The temperature and pressure of the air and fuel are 25
o
C and 101kPa
respectively. The design velocity for each intake is 15 m/s. Determine the
diameter of the air intake line in meters.
CH
4
+a(0.21O
2
+0.79N
2
) bCO
2
+cH
2
O+dN
2

C) 1*1 = b*1 b=1
H) 1*4 = c*2 c=2
O) a*2*0.21 = b*2+c*1 a=9.524

Theoretical air = 9.524 kmol(air)/kmol(fuel)

Theoretical Air
Quiz
One kg/min of methane is burned in a combustor with 25% excess air.
The temperature and pressure of the air and fuel are 25
o
C and 101kPa
respectively. The design velocity for each intake is 15 m/s. Determine the
diameter of the air intake line in meters.
Actual Mass flow rate of air





kg/min 21.5 21.5 * kg/min 1.0 AF * m m
5 . 21
04 . 16
97 . 28
* 9 . 11
M
M
* AF AF
fuel air
fuel
air
= = =
= = =

Actual Air = Theoretical * (1+%excess)
= 9.524*1.25
= 11.9 kmol(air)/kmol(fuel)
Quiz
One kg/min of methane is burned in a combustor with 25% excess air.
The temperature and pressure of the air and fuel are 25
o
C and 101kPa
respectively. The design velocity for each intake is 15 m/s. Determine the
diameter of the air intake line in meters.
Diameter of air intake


m 16 . 0
m 02 . 0 * 4 A 4
D
m 02 . 0
s 60
min 1
*
m/s 15 * kg/m 18 . 1
kg/min 5 . 21
V) (
m
A
AV) ( m
kg/m 18 . 1
1kPa
1kJ/m
* ol 28.97kg/km
298K * K - ol 8.314kJ/km
101kPa
M
T R
P
2
2
3
air
air
air air
3
3
air air
= = =
= = =
=
= = =
t t

Enthalpy: Reacting Systems

Tabular enthalpies inadequate due to arbitrary reference datums
Standard Reference State (Stable Elements): T
ref
= 298.15 K, p
ref
= 1 atm
First Law:
2 2 2 2 2 2
2 2
CO C O CO CO C C O O
CO C O cv
Q m h m h m h n h n h n h
- - - - - - -
= =
2
0 (standard reference state)
C O
h h = =
2
2
2
for CO at 1 atm
cv
CO
f
CO
Q
h h
n
-
-
= =
) ( formation of enthalpy
o
f
h h =
Enthalpy: Reacting Systems
First Law:
( ) ( )
( )
, , ,
f ref ref f
h T p h h T p h T p h h
(
= + = + A

( )
( )
kJ/kmol 387939
kJ/kmol 9364 kJ/kmol 19945 kJ/kmol 393520
) K 298 ( ) K 550 ( kJ/kmol 393520
2
2
2 2 2
=
+ =
= = + =
CO
cv
CO cv
ref CO CO CO cv
n
Q
n Q
T h T h n Q

( ) ( ) ( )
( ) ( ) ( ) 0 0 0 0
2 2
2
2
2
2
2 2
2
2
+ + A + =
A + A + A + =
O C CO
CO
o
f CO cv
O
O
o
f O C
C
o
f C CO
CO
o
f CO cv
n n h h n Q
h h n h h n h h n Q

2 2 2 2
O O C C CO CO cv
h n h n h n Q

=
Standard Reference
State

T
ref
= 25
o
C
P
ref
= 1 atm
Energy Balances: Steady State
( ) ( )
cv
cv
P R f f
e i
e i
P R
F F
Q W
h h n h h n h h
n n
- -
- -
= = + A + A

2 2 2 2 2
3.76 3.76
2 4 4 4
cv
cv
CO H O N F O N
F F
Q W b b b b
ah h a h h a h a h
n n
- -
- -
( (
| | | | | |
= + + + + + +
| | | ( (
\ . \ . \ .

2 2 2
3.76
2 4
P CO H O N
b b
h ah h a h
(
| |
= + + +
| (
\ .

2 2
3.76
4 4
R F O N
b b
h h a h a h
(
| | | |
= + + +
| | (
\ . \ .

Energy Balances: Steady State
( ) ( )
2 2 2 2 2
4 2 2 2 2 2
1*CH 2(O 3.76N ) CO 2H O 2*3.76N
2 2*3.76 2 2*3.76
cv
CO H O N F O N
F
cv
P R
F
f
ref
Q
h h h h h h
n
Q
h h
n
h h h T h T
-
-
-
-
+ + = + +
( (
= + + +

=
(
= +

Energy Balances: Steady State
( ) ( )
( )
( ) ( )
( )
( ) ( ) ( )
| | ( ) | | ( ) ( )
( )
2
2 2
2
2 2
4
-
-
-
2 7.52
169300 15829 4028 2 104040 13494 4258 7.52 11410 3730
289353 Btu/lbmol(fuel)
32210 Btu/lbmol(fuel)
28935
f f
P ref ref ref
N
CO H O
P
N
CO H O
P
f
R
CH
cv
P R
F
h h h T h T h h T h T h T h T
h
h
h h
Q
h h
n
-
-
( (
= + + + +

= + + + +
=
= =
= =
- -
3 32210 257143 Btu/lbmol(fuel) =
Closed System Energy Balance
( ) ( )
P R P R
P R P R
Q W U U nu nu n h RT n h RT = = =

( ) ( )
f f
P R
P R
Q W n h h RT n h h RT = + A + A

Fuel Enthalpies
RP e i
e i
P R
h n h n h =

Enthalpy of Combustion
For Example: A Control Volume at Steady State
( ) ( ) ( ) ( )
( ) ( )
cv
cv
f f f f
e i e i e i
e i
e i e i
P R P R P R
F F
Q W
n h h n h h n h n h n h n h
n n
- -
- -
= + A + A = + A A

LHV
RP
h =
LHV (Lower Heating Value): The enthalpy of combustion when the
reactants and products are at the standard reference state and the
water formed by combustion is a gas

HHV (Higher Heating Value): water formed by combustion is a liquid
Adiabatic Flame Temperature
When no power
produced, and
combustion carried out
adiabatically, T
p

reaches a theoretical
maximum.
When using tables, requires iteration to determine!
( ) ( )
f f
e i
e i
P R
n h h n h h + A = + A

Adiabatic Flame Temperature
( )
( ) ( )
( )
( ) ( )
( )
( ) ( ) ( )
( )
( )
( )
( )
( )
( )
4
2
2 2
2
2 2
-
0
32210 Btu/lbmol(fuel)
2 7.52
169300 4028 2 104040 4258 7.52 3730
?
cv
P R
F
f
R
CH
f f
P ref ref ref
N
CO H O
P
N
CO H O
P R
Q
h h
n
h h
h h h T h T h h T h T h T h T
h h T h T h T
h h
T
-
-
= =
= =
( (
= + + + +

( (
= + + + +

=
=
Fuel Cells
Solid Oxide Fuel Cell Proton Exchange Membrane Fuel Cell
Third Law of Thermodynamics
The absolute entropy of a pure-crystalline
substance at the absolute zero of temperature is
zero.
Clip art courtesy of MS Office 2000
( ) ( )
, ln
i
i i
i
ref
y p
s T p s T R
p
=
Ideal Gas
( )
( )
( )
( )
, , , ,
ref ref
s T p s T p s T p s T p
(
= +

Entropy Balances
Control Volumes at Steady State, Reacting System
2 2 2 2 2
/
0 3.76 3.76
4 4 2 4
cv
j j
F O N CO H O N
j
F F
Q T
b b b b
s a s a s as s a s
n n
o
-
-
- -
( (
| | | | | |
= + + + + + + + + +
| | |
( (
\ . \ . \ .

Closed, Reacting System

P R
b
Q
S S
T
o
o
| |
= +
|
\ .
}
1
P R b F F
Q
ns ns
n T n
o o
| |
= +
|
\ .

}
Chemical Exergy
Total Exergy = Thermo-mechanical Exergy + Chemical Exergy
Thermo-mechanical Exergy
found in Chapter 7
For a Hydrocarbon: C
a
H
b
( )
( )
( ) ( )
2
2 2 2
2 2
/ 4
e
ch
0 0 0 ( ) / 2
e e
e , ln
4 2
a b
O
f O CO H O g a b
CO H O
y
b b
g a g ag g T p RT
y y
+
(
(
| |
(
= + + +
|
(
(
\ .


Chemical Exergy
For Carbon Monoxide: CO

( )
( )
( )
2
2 2
2
1/ 2
e
ch
0 0 0
e
1
e , ln
2
O
CO O CO
CO
y
g g g T p RT
y
(
(
(
= + +
(
(


For Water: H
2
O
( )
( )
2 2
2
ch
0 0 0 ( ) ( )
e
1
e , ln
H O l H O g
H O
g g T p RT
y
(
(
= + (

(

For N
2,
O
2
, CO
2
( )
ch
0
e
1
e ln RT
y
(
= (
(

For mixture of gas phases
of Ideal Gases at T
0
, p
0
ch
0
e
e ln
i
i
i
i
y
RT y
y
| |
=
|
\ .

Exergy Summary
( ) ( ) ( )
2
ch
0 0 0 0 0
e e
2
V
u u p v v T s s gz = + + + +
( ) ( )
2
ch
f 0 0 0
e e
2
V
h h T s s gz = + + +