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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
Undesirable combustion phenomenon knock
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
Composition of air
44.009
Fuels
Blends of many different hydrocarbons
Predominantly hydrogen (~14% by mass) & carbon (~86% by mass)
Diesel fuel can contain some sulfur (~1%)
Biodiesel fuel FAME made from vegetable oil or animal fat
Alcohol fuels contain some oxygen (methanol, ethanol)
CNG, LPG
Appendix D, page 915 in Heywood contains data on many different 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
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
Fuel composition
Gravimetric composition is given by mass fractions of C and H in the fuel.
Atomic composition is given by numbers of atoms of C and H in fuel
molecule: CaHb
Atomic composition can be determined from gravimetric and vice versa
notes
notes
b
C a H b a O 2 3.773N 2 aCO 2 H 2O 3.773 a N 2
4
2
A Fs
12.011a 1.008b
or
A Fs
a b 4 4.77 28.97
12a b
notes
notes
Example
A hydrocarbon fuel of composition 84.1 percent by mass C and 15.9 percent by
mass H has molecular weight of 114.15. Determine the number of moles of air
required for stoichiometric combustion and the number of moles of products
produced per mole of fuel. Calculate (A/F)s, (F/A)s, and the molecular weight of
the reactants and products
notes
A F s F A a
A F a F A s
Equivalence ratio
Relative ratio
Fuel - lean
1
Stoichiometric 1
Fuel-rich
1
1
1
1
notes
notes
notes
Gas analysis
In IC engines combustion is never complete
Gas analysis is used to determine composition of combustion product
experimentally
Given in mole fractions (per cent, ppm) unless otherwise stated
Differentiate wet and dry gas analysis
notes
notes
Example
notes
Example
A fuel has the following gravimetric composition
hexane (C6H14)
octane (C8H18)
cyclohexane (C6H12)
benzene (C6H6)
40%
30%
25%
5%
Example
A fuel has a composition by weight of 0.865 carbon, 0.133 hydrogen and 0.002
incombustibles. Find the stoichiometric air/fuel ratio.
When the fuel is burnt with excess air, the dry volumetric exhaust gas analysis is: CO 2
0.121, N2 0.835, O2 0,044. Determine actual air/fuel ratio used and the wet volumetric gas
analysis.
Example
The results of a dry gas analysis of an engine exhaust are as follows: CO 2 10.1%, N2 82.6% .
Calculate gravimetric composition of fuel.
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
notes
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
Back to 3.2
ni h 0f ,i
Example 3.2
Calculate the enthalpy of the products and reactants, and heat of
reaction at constant pressure and constant volume, of a
stoichiometric mixture of methane and oxygen at 298,15 K
solution
notes
Energy of reactants
and products
R.Stone, Introduction to
internal combustion engines
notes
Example
In a closed combustion vessel propane (C3H8) and air with
an equivalence ratio of 1.11 initially ant 25C burn to
produce products consisting solely of carbon dioxide
(CO2), carbon monoxide (CO), water (H2O) and
atmospheric nitrogen.
If the heat rejected from the vessel is 820 MJ per kmol of
fuel, find the final temperature.
If the initial pressure is 1 bar, estimate the final pressure.
solution
notes
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
notes
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
notes
Chemical Equilibrium
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
notes
Chemical equilibrium
Combustion products of hydrocarbon fuels at low
temperatures are: N2, H2O, CO2, and O2 or CO and H2
At higher temperatures (> about 2200 K), dissociation
occurs. 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. notes
notes
H T S G 0
At equilibrium
G p ,T
notes
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
notes
G p ,T i ni
(a )
G
i
ni
For ideal gas
p ,T , n j j i
pi
i T RT ln
p0
0
i
notes
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
notes
Equilibrium constant
If equilibrium constant is known, partial pressure of
components can be determined
Equilibrium constant is function of temperature only
It is tabulated
notes
Equilibrium constant
back to ex.3.4
back to ex.3.5
notes
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
notes
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
1
CO O 2 CO 2
2
From table
notes
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
notes
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
notes
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
notes
Example 3.4
The equilibrium relation gives
nP p0
12
2 pP
1
12
27.5
0.0074
notes
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
notes
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.
notes
Example 3.5
Solution:
Combustion reaction:
C8 H18
12.5
O2 3.773N 2 aCO2 bH 2O cCO dH 2 39.30N 2
1.2
ac 8
2b 2d 18
2a b c 20.83
notes
Example 3.5
Water-gas reaction
CO 2 H 2 CO H 2 O
bc p
Kp
ad np0
or
bc
Kp
ad
notes
Example 3.5
Water gas reaction:
CO 2 H 2 CO H 2O
From table
notes
Example 3.5
Water gas reaction:
CO 2 H 2 CO H 2O
From table
Then
and
log10 K p 0.53
K p 3.388
bc
3.388
ad
notes
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
notes
Simultaneous reactions
notes
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
notes
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
notes
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
notes
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
notes
where:
p SC SO
p SO S N
SC S H
notes
Some results
back
notes
back
notes
Back to Ex
back
notes
Back to Ex
back
notes
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
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
1.25
0 .8
Example 3.2
Calculate the enthalpy of the products and reactants, and heat of
reaction at constant pressure and constant volume, of a
stoichiometric mixture of methane and oxygen at 298,15 K
CH 4 2O 2 CO 2 2H 2O
table
Example 3.2
Calculate the enthalpy of the products and reactants, and heat of
reaction at constant pressure and constant volume, of a
stoichiometric mixture of methane and oxygen at 298,15 K
CH 4 2O 2 CO 2 2H 2O
U V 801.3 MJ kmol CH 4
CH 4
table
MJ kmol CH 4
back
back
Actual reaction
notes
back
Actual reaction
C3H 8 4.5 O 2 3.77N 2 2CO 2 CO 4H 2O 5 16.93N 2
First law
QR P U P U R
notes
back
850 820
therefore T 1700 K
tables
back
699 820
notes
back
back
pR
105
For the products
nP RTP 2 1 4 16.93 R 1800
pP
notes
back
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
Ca 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 2O 3.773 12.5N 2
AFs
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
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
U P T U P T0 U R T U R T 0 U V ,T
0
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
notes
Example
A fuel has the following composition
pentane (C5H12)
heptane (C7H16)
octane (C8H18)
dodecane (C12H26)
benzene (C6H6)
10% by mass
30% by mass
35% by mass
15% by mass
10% by mass
Calculate gravimetric composition of the fuel and air fuel ratio for equivalence ratio of 1.1
notes