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Combustion
Premixed Nonpremixed Partially premixed
Carbureted SI engine
Diesel Engine
Gas Turbine?
REACTING MIXTURES AND COMBUSTION
ME 306 Applied Thermodynamics
Reacting Mixtures and Combustion
Introducing Combustion
Chemical reactions
Stoichiometric coefficient
Air to fuel ratio
Theoretically correct A:F ratio: equivalence ratio
Determining products of combustion

Conservation of EnergyReacting Systems
Enthalpy of formation
Enthalpy of reaction
Enthalpy of combustion

Equilibrium constant
2
Thermo-chemistry
Chemical Reaction: bonds are broken, new bonds are formed
Mixture of Gases:
Each species is a perfect gas
Mixture satisfies Daltons law of partial pressure
Average Molecular weight

Specific heat of a mixture

NASA polynomial fits are used
Similarly one can get Internal energy, Enthalpy, Entropy etc
3
1
s
N
i
i
p p
=
=

1
1
1 1
1
( / )
Also 1
s
s
s s
N
i i N
i
i i
i
N N
i i
i i
W X W
Y W
X Y
=
=
= =
= =
= =

2 2
C O CO +
, ,
1
s
N
p mix p i i
i
c c X
=
=

, 2 3 4
1, 2, 3, 4, 5,
p i
i i i i i
c
A A T A T A T A T
R
= + + + +
mass fraction may be
calculated with the known
mole fraction and vice versa
Mole and Mass fractions
4
4 2 2
3 CH O H O + +
Find the mole and mass fractions for the following mixture
CH
4
and air are mixed in the volume ratio of 1:1; find the mole and
mass fractions of each species
Complete and Incomplete combustion
Complete combustion
5
2 2 2
2 2 H O H O +
Combustion is complete when all the carbon present in the fuel is burned to
carbon dioxide, all the hydrogen is burned to water, all the sulfur is burned to
sulfur dioxide, and all other combustion combustible elements are fully oxidized.
When these conditions are not fulfilled, combustion is incomplete.
4 2 2 2
2 2 CH O CO H O + +
2
C O CO O + +
Incomplete combustion
Stoichiometry
General chemical reaction may be represented as
6
2 2 2
2 2 H O H O +
' ''
1 1
s s
N N
i i i i
i i
A A v v
= =

i 1 2 3
A
i
H
2
O
2
H
2
O
2 1 0
0 0 2
'
i
v
''
i
v
Reactants are completely
converted into products
2 2 2 2
2 2 2 H O H O O + +
1 mole of reactant O
2
is left as un-
reacted;
Not a stoichiometric mixture
Theoretical Fuel to Oxidiser ratio = (2 2) /(1 32) 0.125 =
Atom balance
2 2 2 2 2 2
2 0 0 0 2 H O H O H O H O + + + +
7
2 2 2 2
2 2 2 H O H O O + +
( )
/
(2 2) /(2 32)
Equivalence Ratio = 0.5
( / ) (2 2) /(1 32)
act
th
F O
F O

= =

Fuel lean
2 2 2
2 2 H O H O +
Equivalence ratio is unity
( )
/
Equivalence Ratio =
( / )
act
th
F O
F O
7 16 2 2 2 2 2
11 (11 3.76) 7 8 (11 3.76) C H O N CO H O N + + + +
12 7+16
Theoretical Fuel to Air ratio = 0.0662
(11 32) (11 3.76 28)

=
+
Theoretical Air to Fuel ratio = 15.1:1
8
DETERMINING PRODUCTS OF COMBUSTION
DRY PRODUCT ANALYSIS
Orsat analyzer, gas chromatograph etc.

Usually measurements are given on the dry basis i.e except water
Numerical problem
Methane, CH
4
, is burned with dry air. The molar analysis of the products on a dry basis is
CO
2
, 9.7%; CO, 0.5%; O
2
, 2.95%; and N
2
, 86.85%. Determine (a) the airfuel ratio on both a
molar and a mass basis, (b) the percent theoretical air
Heat of formation
Heat absorbed when one kmol of substance is formed from its constituent elements
in their standard state at 298.15 K and 1 atm, through a (p,T) = const process.
Heat of formation of all elements in their most naturally occurring states is assigned
as zero (by convention)
9
0
( ) 2( ) 2( )
; 393,520 kJ/kmol
s g g f
C O CO H + A =
0
2( ) ( )
1
; 218000 kJ/kmol
2
g g f
H H H A =
( ) 2( ) 2( )
1
; This is not a formation reaction
2
g g g
CO O CO +
Not an
element
( ) ( ) 2( )
2 ; This is not a formation reaction
s g g
C O CO +
Not in
standard
state
exothermic
endothermic
Heat of formation
10
2 2
C O CO +
Enthalpy of formation will be negative for an exothermic reaction and vice versa
Enthalpy at any other state is given by
Sensible enthalpy
change
Heat of Reaction
11
per mol basis
Heat of Reaction
12
PROBLEM:
Methane gas at 400 K and 1 atm enters a combustion chamber, where it is mixed with
theoretically correct air entering at 500 K and 1 atm. The products of combustion exit at 1800 K
and 1 atm. For operation at steady state, determine the rate of heat transfer from the
combustion chamber in kJ per kmol of fuel. Neglect kinetic and potential energy effects. The
average value for the specific heat of methane between 298 and 400 K is 38 kJ/kmol K.
for products
for air
Reactions at Constant Volume
13
PROBLEM:
A mixture of 1 kmol of gaseous methane and 2 kmol of oxygen initially at 298 and 1 atm
burns completely in a closed, rigid container. Heat transfer occurs until the products are
cooled to 900 K. If the reactants and products each form ideal gas mixtures, determine (a)
the amount of heat transfer, in kJ, and (b) the final pressure, in atm.
Heating Value
14
Heating value of a fuel is a positive number equal to the magnitude of the enthalpy of
combustion.

Higher Heating Value (HHV): obtained when all the water formed by combustion is a liquid

Lower heating value (LHV): obtained when all the water formed by combustion is a vapor.

The higher heating value exceeds the lower heating value by the energy that would be required
to vaporize the liquid formed.
PROBLEM:
Calculate the enthalpy of combustion of gaseous methane, in kJ per kg of fuel, (a) at
298 K, 1 atm with liquid water in the products, (b) at 298 K, 1 atm with water vapor in
the products.
If all the heat released in a combustion reaction goes into raising the
temperature of the products, then the resulting temperature is called Adiabatic
Flame Temperature, T
f
. This is the theoretically maximum temperature.

15
PROBLEM:
Liquid octane at 298 K, 1 atm enters a well-insulated reactor and reacts with air entering at the
same temperature and pressure. For steady-state operation and negligible effects of kinetic and
potential energy, determine the temperature of the combustion products for complete
combustion with (a) the theoretical amount of air, (b) 400% theoretical air.
Reaction progress variable
16
- ; etc.
A A C C
dn dn o v o v
By mass balance, proportionality
constant must be same for all species
Small change in number of moles
c is known as extent of reaction or reaction progress variable 0 s c >1
c = 0 at the beginning and c = 1 when products are fully formed
A B C D
A B C D v v v v + +
C A B D
A B C D
dn dn dn dn
dc
v v v v

= = = =
= - ; = -
= ; =
A A B B
C C D D
dn d dn d
dn d dn d
v c v c
v c v c
Gibbs free energy
17
0 for reversible process
0 for irreversible process
dG
dG
=
<
Hence
G H TS =
Thermodynamics extensive property
dG dH TdS SdT
H U PV dH dU PdV VdP
=
= + = + +
dG dU PdV VdP TdS SdT = + +
For a constant pressure and
temperature process
dG dU PdV TdS = +
0 dG dQ TdS = s
From second law of
thermodynamics
Equilibrium constant
18
Reaction proceeds in the
direction such that Gibbs free
energy continues to decrease
and reaches minimum at the
equilibrium state
( ) ( )
( ) ( )
0
/ /
exp ( )
/ /
C D
A B
C ref D ref
T
A ref B ref
p p p p
G
K T
RT
p p p p
v v
v v
| | A
= =
|
\ .
Equilibrium constant
Not derived here;
Ref any standard combustion
books for this derivation
0
prod reac
G G G A =
0 0 0 0
0
C D A B C D A B
G g g g g v v v v A = + +
0
exp ( )
C D A B
C D
A B
C D T
A B ref
X X G p
K T
X X p RT
v v v v
v v
v v
+
| |
| | A
= =
|
|
|
\ .
\ .
c
Equilibrium constant
19
2 2
1
2
CO CO O +
2
2 2
2
1/ 2 1
1/ 2 1 1 1/ 2 1 1
1
.
( ) . .
o co
p o co co
co
X X
K T p p p p
X
+
= =
C D A B
C D A B v v v v + +
p
ref
= 1 atm
For the reverse reaction
Example
0
ln ln ( )
C D A B
C D
A B
C D T
A B ref
X X G p
K T
X X p RT
v v v v
v v
v v
+
(
| |
A
(
= =
|
|
(
\ .

*
ln ( ) ln ln ( )
A B C D
A B
C D
A B
C D ref
X X p
K T K T
X X p
v v v v
v v
v v
+
(
| |
(
= =
|
|
(
\ .

Reciprocal of each
other