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TOPIC
Thermochemistry of
fuel-air mixtures
Characterization of flames
Combustion of the fuel-air mixture controls engine power, efficiency and
emissions.
Combustion phenomena are different for spark-ignition engines and diesels
Combustion phenomena
In spark-ignition engines:
fuel is mixed with air in the intake system
spark initiates the combustion
flame develops from the kernel created by spark discharge and
propagates across the cylinder to combustion chamber walls
at the walls, the flame is quenched or extinguished
Combustion phenomena
In diesels:
fuel is injected into the cylinder near the end of compression process
fuel is self ignited by hot air
burning then proceeds as fuel and air mix
Flames classification
Characterization of flames
The conventional spark-ignition flame is a premixed unsteady turbulent
flame, and the fuel-air mixture through which the flame propagates is in the
gaseous state
The diesel engine combustion process is unsteady turbulent diffusion flame,
and the fuel is initially in the liquid phase
pV mRT nRT
Fuels
Actually blends of many different hydrocarbons
Predominantly hydrogen (~14% by mass) & carbon (~86% by mass)
Diesel fuel can contain some sulfur (~1%)
Alcohol fuels contain some oxygen
Fuel composition
Gravimetric composition is given by mass fractions of C and H in the fuel.
Used for liquid fuels
Combustion stoichiometry
Going from reactants (fuel + air) to products
Depends only on conservation of mass for each atom
Done on a per kmole of fuel basis
3 1 b
Hydrogen balance: 8 2 c c 4
Oxygen balance:
2a 2b c a
C3 H8 5O 2 3CO2 4H 2O
23 4
5
2
Complete combustion
Enough oxygen to completely oxidize (burn) the fuel
All carbon oxidizes to CO2 , all hydrogen to H2O
O2 is used to form H2O first, then the rest is used to form CO
Any leftover O2 then converts CO into CO2
Composition of air
General stoichiometry
Approximate a fuel with a carbon atoms and b hydrogen atoms
b
b
b
C a H b a O 2 3.773N 2 aCO 2 H 2O 3.773 a N 2
4
2
4
AFs
Example 1
Octane (C8H18) is burned with the stoichiometric amount of air.
Calculate the AF and the molecular weights of the reactants and the products, as
well as the dew-point temperature of the products.
Example 1
Octane (C8H18) is burned with the stoichiometric amount of air.
Calculate the AF and the molecular weights of the reactants and the products, as
well as the dew-point temperature of the products.
a 8 b 18
b
b
b
C a H b a O 2 3.773N 2 aCO 2 H 2O 3.773 a N 2
4
2
4
C8 H18 12.5 O 2 3.773N 2 8CO 2 9H 2 O 3.773 12.5N 2
AFs
15.12
kg of air
kg of fuel
Example Reactants
nr 1 12.5 1 3.773 60.7 kmole
yC8H18 1 60.7 0.017
yO 2
yN2
M r 29.1
kg
kmol
Example Products
n pr 8 9 47.2 64.2 kmole
yCO2 8 64.2 0.125
yH2O 9 64.2 0.140
yN2 47.2 64.2 0.735
M pr yi M i 0.125 44.011 0.140 18.016 0.735 28.16
pr
M pr 28.7
kg
kmole
Excess air
b
Ca H b s O 2 3.773N 2 aCO 2 H 2O xO 2 3.773 s N 2
2
s a
b
4
2 x 2 s 2a
b
b
2 s a 2 s 1
2
4
b
Ca H b s O 2 3.773N 2 aCO 2 H 2O s -1 O 2 3.773 s N 2
2
s 32 3.773 28.16
AFa
12.01a 1.008b
AFs
s 32 3.773 28.16
12.01a 1.008b
AFs FAa 1
AFa FAs
Equivalence ratio
Relative ratio
Stoichiometric
Fuel-rich
b 18
1.25
b
Ca Hb s O 2 3.773N 2 aCO 2 H 2O s -1 O 2 3.773 s N 2
2
C8 H18 15.625 O 2 3.773N 2 8CO 2 9H 2 O 3.125O 2 59N 2
AFa
18.9
kg air
AFs
kg fuel
Reactants
nr 1 15.625 1 3.773 75.6 kmole
yC8H18 1 75.6 0.013
yO2 15.625 75.6 0.207
yN2 59 75.6 0.780
M r yi M i 0.013 34.232 0.207 31.998 0.780 28.16
r
M r 29.0
kg
kmole
kg
29
.
1
kmol
Products
n pr 8 9 3.125 59 79.1 kmole
yCO2 8 79.1 0.101
yH2O 9 79.1 0.114
yO2 3.125 79.1 0.040
yN2 59 79.1 0.745
M pr yi M i 0.101 44.011 0.114 18.016
pr
kg
kmole
kg
28
.
7
kmole
Dewpoint temperature
yH2O 0.114
pv yH2O p 0.114 101.33 11.55 kPa
Tdp Tsat pv 48o C
52.7 C
o
1.25
0 .8
QR P WR P U P U R
QR P U P U R U V ,T
QR P p VP VR U P U R
QR P U P pVP U R pVR H P H R H p ,T
H p ,T heat of reaction at constant pressure at temperature T
H p ,T U V ,T R
n P nR T
U V ,T ,H Oliq U V ,T ,H O vap
2
mH2Ou fg H2O
Enthalpy of formation
Enthalpy of products at standard
reference state
H P0
ni h 0f ,i
products
H R0
reactants
ni h 0f ,i
Example 3.2
Calculate the enthalpy of the products and reactants, and the
enthalpy increase and internal energy increase of the reaction, of a
stoichiometric mixture of methane and oxygen at 298,15 K
CH 4 2O 2 CO 2 2H 2O
MJ kmol CH 4
U V H p R nP nR T0 H p 801.3 MJ kmol CH 4
0
MJ kmol CH 4
Heating values
Heating value of a fuel is the magnitude of the heat of reaction at
constant pressure or at constant volume at standard temperature for
the complete combustion of unit mass of fuel
QHV p H p ,T
QHVV U V ,T
QHHVp QLHVp
mH2O
h fg H2O
mf
U P T U P T0 U R T U R T 0 U V ,T
0
Energy of reactants
and products
Find molar enthalpy of N2 at 400 K
R.Stone
Actual reaction
C3 H8 4.5 O 2 3.77N 2 2CO 2 CO 4H 2O 5 16.93N 2
First law
QR P U P U R
850 820
therefore T 1700 K
699 820
p
105
Combustion efficiency
Net chemical energy release due to combustion at constant pressure
H R TA H P TA m
ni h
0
f ,i
i , reactants
H R TA H P TA
m f QHV
ni h
i , products
0
f ,i
Combustion efficiency
Chemical equilibrium
Consider carbon dioxide in a vessel
At high temperature some of the CO2 molecules dissociate
into CO and O2 molecules
If the mixture of CO2, CO, and O2 is in equilibrium, then
CO2 molecules are dissociating into CO and O2 at the same
rate as CO and O2 molecules are recombining in the
proportions required to satisfy the equation
1
CO O 2 CO 2
2
Chemical equilibrium
In combustion products of hydrocarbon fuels, the major
species present at low temperatures are N2, H2O, CO2, and
O2 or CO and H2.
At higher temperatures (> about 2200 K), these major
species dissociate and react to form additional species
Molar equilibrium composition of the products of adiabatic
combustion of stoichiometric mixture of petrol is:
N2 ~ 0.7;
H2O, CO2 ~ 0.1;
CO,
OH, O2, NO, H2 ~ 0.01;
H, O ~
0.001; and other species in lesser amounts.
H T S G 0
At equilibrium
G p ,T
a M a b M b ... l M l m M m ...
In concise form
M
i
By convention
i
is negative
for reactants, and positive for products
Let an amount na of M a react with nb of M b , etc.,
and produce nl of M l , nm of M m , etc. These amounts
are in proportion
ni i n
G p ,T i ni
i
G
i
ni
For ideal gas
p ,T , n j j i
pi
i T RT ln
p0
0
i
(a )
pi
T RT ln p i n 0
0
pi
ln p
0
0
i
T
0
i
RT
G T
0
RT
ln K p
Equilibrium constant
If equilibrium constant is known, partial pressure of
components can be determined
Equilibrium constant is function of temperature only
It is tabulated
Equilibrium constant
back to ex.3.4
back to ex.3.5
Example 3.4
A stoichiometric mixture of CO and O2 in a closed vessel,
initially at 1 atm and 300 K, is exploded. Calculate the
composition of the products of combustion at 2500 K and the
gas pressure
Combustion equation
From table
Then
1
CO O 2 CO 2
2
log10 K p 1.440
K p 27.54
Example 3.4
If the degree of dissociation in the products is
(i.e., a fraction of the CO2 formed by complete combustion
is dissociated), the product composition is
CO 2 , 1 ;
CO, ;
O2 ,
2
nP 1 2
Example 3.4
The ideal gas law gives
pRV nR RTR
pPV nP RTP
Thus
pP
1 2500
5.556 1 mol
nP p0 1.5 300
Example 3.4
The equilibrium relation gives
nP p0
12
2 pP
1
12
0.0074
27.5
Example 3.4
Composition of products in mole fractions
xCO2
0.893
nP
xCO
0.071
nP
2
xO2
0.037
nP
Pressure of the product mixture
Example 3.5
In fuel-rich combustion product mixtures, equilibrium between
the species CO2, H2O, CO, and H2 is often assumed to determine
the burned gas composition. For = 1.2 , for C8H18 air
combustion products, determine the mole fractions of the product
species at 1700 K.
Example 3.5
Solution
The reaction relating these species (often called the water gas
reaction) is
CO 2 H 2 CO H 2O
From table
log10 K p 0.53
Then
K p 3.388
Example 3.5
Combustion reaction
12.5
C8 H18
O2 3.773N 2 aCO 2 bH 2O cCO dH 2 39.30N 2
1.2
Carbon balance gives:
ac 8
2b 2d 18
2a b c 20.83
Example 3.5
Water-gas reaction
CO 2 H 2 CO H 2 O
bc p
Kp
ad p0
or
bc
3.388
ad
Example 3.5
Four equations are solved for c
c 2 19.3c 47.3 0
which gives
c 2.89,
a 5.12,
b 7.72,
d 1.29
a b c d 39.3 56.3
and the mole fractions of the species in the burned gas mixture are
CO2, 0.0908;
H2O, 0.137;
CO, 0.051;
H2, 0.023;
N2, 0.698
Simultaneous reactions
Consider mixture of N reacting gases in equilibrium
If there are C chemical elements, conservation of elements will
provide C equations which relate the concentrations of N species
Set of (N C) chemical reactions, each in equilibrium, which
includes each species at least once will provide additional
equations required to determine concentration of each species in
the mixture
Complete set of equations is a coupled set of C linear and (N C)
nonlinear equations
This set of equations is difficult to solve when (N C) > 2
Species to be considered:
O,
O 2 , O3 ,
H,
H 2,
OH,
CH 4
C 2H 2
O3
1
N2
2
NO
NO
10
2H 2 O 2
1
1
O 2 H 2 OH
2
2
CO 2 C O 2
5
6
1
NO O 2
2
1
3
NH 3
N2 H2
2
2
NO 2HNO3 3NO 2 H 2 O
HCN
2H 2 O
CO
1
C O2
2
NO 2
1
1
N2 H2
2
2
11
12
13
14
Equation of equilibrium
1
O2 O
2
3
O 2 O3
2
1
H2 H
2
2H 2 O 2H 2 O 2
K1 pO pO1 22
K 2 pO3 pO3 22
K 3 pH p1H22
1
1
O 2 H 2 OH
2
2
CO 2 C O 2
K 6 pC pO2 pCO2
K 7 pC p1O22 pCO
CO
1
C O2
2
Equation of equilibrium
K8 pC pH2 2 pCH 4
1
N2 N
2
NO N O
K 9 pN p1N22
10
K10 pN pO pNO
1
NO O 2
2
1
3
NH 3
N2 H2
2
2
NO 2HNO3 3NO 2 H 2 O
11
12
13
3
2
K13 pNO
pH 2O pHNO
pNO
2
3
14
CH 4
C 2H 2
NO 2
HCN
1
1
N2 H2
2
2
where:
p SC SO
p SO S N
SC S H
Some results
p p
xi
i
p0 p0
i
i
i
x
i Kp
i
If
i 0 changes in pressure have no effect on the
i
composition.
If
i 0 (dissociation reaction), then the mole
i
fractions
of the dissociation products decrease as pressure
increases.
i 0 (recombination reaction), the converse is true.
If