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PV mRT m
T nR T
where R is the Universal Gas Constant (8.314 kJ/kmol K), M is the molecular
weight (29 kg/kmol for air) and n is the number of moles.
In combustion one deals with mixtures of gases such as fuel vapour and air.
The mass m of a mixture is equal to the sum of the mass of all n components
n
m mi
i 1
and
xi 1
i 1
U mu mi ui
H mh mi hi
i 1
i 1
The specific internal energy u and enthalpy h of the mixture (units: kJ/kg) is:
n
u xi ui
h xi hi
i 1
i 1
n ni
i 1
and
yi 1
i 1
M yi M i
i 1
U ni ui
H ni hi
i 1
i 1
u yi ui
h yi hi
i 1
i 1
The partial pressure of a component, Pi, in the mixture (units: kPa) is:
Pi yi P
or
yi
ni Pi
n P
s R ln P Po xi sio Ri ln(Pi / P )
i 1
s R ln P Po yi sio Ri ln yi
i 1
Note, if the mixture pressure is at 1 bar then the first terms drops out.
5
n N 2 ntot
1
0.79
3.76
ntot nO2
0.21
M air yi M i yO2 M O2 y N 2 M N 2
i 1
mH 2O
mair
PH 2O
Psat (T )
mH 2O
mair
M H 2O nH 2O
M air nair
PH 2O
PH 2O
0.62 Psat (T )
0.62
0.62
P P (T )
P PH O
sat
Pair
mH 2O
M H 2O
nH 2O
mair nair M air nair
1.61
M H 2O
M H 2O
0.62
nair
7
n= 1 CH4 methane
n= 2 C2H6 ethane
n= 3 C3H8 propane
n= 4 C4H10 butane
n= 8 C8H18 n-octane and isooctane
H
H
methane
propane
n-octane
H
C
propene
acetylene
For alcohols one hydroxyl (OH) group is substituted for one hydrogen
e.g. methane becomes methyl alcohol (CH3OH) also known as methanol
ethane becomes ethyl alcohol (C2H5OH) also known as ethanol
9
Combustion Stoichiometry
If sufficient oxygen is available, a hydrocarbon fuel can be completely
oxidized, the carbon is converted to carbon dioxide (CO2) and the hydrogen is
converted to water (H2O).
The overall chemical equation for the complete combustion of one mole of
propane (C3H8) is:
C3 H 8 aO2 bCO2 cH 2O
# of moles
species
Combustion Stoichiometry
Air contains molecular nitrogen N2, when the products are low temperature
the nitrogen is not significantly affected by the reaction, it is considered inert.
The complete reaction of a general hydrocarbon CH with air is:
The above equation defines the stoichiometric proportions of fuel and air.
11
Combustion Stoichiometry
The stoichiometric mass based air/fuel and fuel/air ratio is:
A/ F s
( F / A) s
3
.
76
O2
M N2
4
4
M C M H
Substituting the respective molecular weights and dividing top and bottom
by one gets the following expression that only depends on the ratio of the
number of hydrogen atoms to hydrogen atoms () in the fuel.
A/ F s
( F / A) s
4
12 1
12
13
14
Off-Stoichiometric Mixtures
The equivalence ratio, , is commonly used to indicate if a mixture is
stoichiometric, fuel lean, or fuel rich.
A/ F s
F / A mixture
A / F mixture
F / A s
stoichiometric = 1
fuel lean
<1
fuel rich
> 1
Stoichiometric mixture:
Off-stoichiometric mixture:
1
4
15
Off-Stoichiometric Conditions
Other terminology used to describe how much air is used in combustion:
150% stoichiometric air = 150% theoretical air = 50% excess air
C3 H 8 ( )(O2 3.76 N 2 )
1.5 mixture is fuel lean
4
Example: Consider a reaction of octane with 10% excess air, what is ?
The stoichiometric reaction is:
C8 H18 12.5(O2 3.76 N 2 ) 8CO2 9 H 2O 47 N 2
10% excess air is:
C8 H18 1.1(12.5)(O2 3.76 N 2 ) 8CO2 9 H 2O aO2 bN 2
16 + 9 + 2a = 1.1(12.5)(2) a = 1.25,
b = 1.1(12.5)(3.76) = 51.7
A/ F s
12.5(2)(4.76) / 1
0.91
A / F mixture 1.1(12.5)(2)(4.76) / 1
16
Products
W
Q
Reactants
State 1
Products
State 2
Reaction
Applying First Law with state 1 being the reactants at P1, T1 and state 2
being products at P2, T2:
Q U W
Q12 (U 2 U1 ) P (V2 V1 )
17
HP < H R
Q<0
exothermic reaction
HP > H R
Q>0
endothermic reaction
18
Enthalpy of Reaction
Consider the case where the final temperature of the products is the same as
the initial temperature of the reactants (e.g., calorimeter is used to measure Q).
W
To
Reaction
P1=P2=Po
T1=T2=To
19
Heat of Combustion
The maximum amount of energy is released from a fuel when reacted with a
stoichiometric amount of air and all the hydrogen and carbon contained in the
fuel is converted to CO2 and H2O
20
Heat of Combustion
There are two possible values for the heat of combustion that can be calculated
depending on whether the water in the products is taken to be in a liquid or
vapour state.
T
hf
hg
Tp
HR = HP HR < 0 (exothermic)
The term higher heat of combustion is used when the water in the products
is taken to be in the liquid state
The term lower heat of combustion is used when the water in the products
is taken to be in the vapour state
21
Heat of Formation
Consider the following reactions taking place at atmospheric pressure and
with TP = TR = 298K
1 / 2O2 ( g ) H 2 ( g ) H 2O(l )
C ( s ) O2 ( g ) CO2 ( g )
Q 286,000 kJ / kmol H 2O
Q 394,000 kJ / kmol CO2
In these reactions H2O and CO2 are formed from their elements in their
natural state at standard temperature and pressure (STP) 1 atm and 298K.
Reactions of this type are called formation reactions and the corresponding
measured heat release Q is referred to as the standard heat of formation
o
h
and takes the symbol f so:
hf,oH 2O 286,000 kJ / kmol
hf,oCO2 394,000 kJ / kmol
Values for standard heat of formation for different species are tabulated
22
at STP
23
Q hH 2O (l ) 1 / 2hO2 ( g ) hH 2 ( g ) h f , H 2O (l )
hH 2O (l ) h f , H 2O (l )
sensible enthalpy
T
298
K c p ,i dT
25
Reaction
P2=Pa
T2=Ta
For a constant pressure process, the final products temperature, Ta, is known
as the adiabatic flame temperature (AFT).
Q ni hi (T p ) ni hi (TR ) 0
P
ni hi (Ta ) ni hi (T1 )
P
For a given reaction where the nis are known for both the reactants and the
products, Ta can be calculated explicitly.
26
o
o
ni h f ,i hi (Ta ) hi (298K ) ni h f ,i hi (T1 ) hi (298K )
P
P
R
R
o
OR
Ta
Ti
c p ,i dT ni 298
c p ,i dT ni h fo,i ni h fo,i
ni 298
P
P
R
R
H Ro
o
o
ni hi (Ta ) ni hi (T1 ) hi (298K ) ni h f ,i ni h f ,i ni hi (298K )
P
P
P
R
R
27
P
R
h fo,O2 h fo, N 2 0
Ta,
29
30
31
Reaction
P2=PCV
T2=Ta
Q ni ui (T p ) ni ui (TR ) 0
P
ni ui (Ta ) ni ui (T1 )
P
Note h = u + pv = u + RT, so
ni (hi (Ta ) R T ) ni(hi(T1 ) R T)
P
32
o
o
ni h f ,i hi (Ta ) hi (298K ) R Ti ni h f ,i hi (T1 ) hi ( 298K ) R Ti
P
o
o
ni hi (Ta ) ni hi (T1 ) hi ( 298K ) ni h f ,i ni h f ,i ni hi (298K )
R
P
P
P
R
ni R Ta ni R T1
p
The AFT for a constant volume process is larger than for a constant pressure
process.
The AFT is lower for constant pressure process since there is Pdv work done
33
PR
Pp
np
PR nR
Pp
Tp
TR
PCV n p
Pi nR
Ta
Ti
For large HCs the mole ratio term is small, e.g., for stoichiometric octane
air
C8 H18 12.5(O2 3.76 N 2 ) 8CO2 9 H 2O 47 N 2
PCV n p
Pi
nR
Ta 64 Ta
T
1.06 a
Ti 60.5 Ti
Ti
Chemical Equilibrium
In general the combustion products consist of more than just CO 2, H2O
O2, and N2
For rich mixtures CO also exists in the products and at high temperatures
the molecules dissociate to form H, O, OH, NO via the following reactions:
H 2 2H
O2 2O
H 2 O2 2OH
O2 N 2 2 NO
2O O2
2OH H 2 O2
2 NO O2 N 2
At equilibrium the rate of the forward reaction equals the rate of the
backward reaction.
H 2 2H
O2 2O
H 2 O2 2OH
O2 N 2 2 NO
35
Chemical Equilibrium
At equilibrium the relative proportion of the species mole fraction is fixed
For the general equilibrium reaction
n A A nB B ncC nD D
The equilibrium composition for species CD is given by:
X
K (T )
X
nC
C
nA
A
X
X
nD
D
nB
B
P
ref
nC nD n A nB
Chemical Equilibrium
Recall that for a rich mixture (<1) the reaction equation could not be
balanced (5 unknowns a, b, d, e, f and only 4 atom balance equations for
C,H,O,N ) even if we neglect dissociation (i.e., low product temperature)
X CO X H O
2
X CO X H
2
eb
a f
P 1 atm
1 = a+c
3 = a+b+2c+2d
1 = b+2e
c=1-a
d = 1/2(1 + a - b)
e = 1/2(1 - b)
CO2 CO 1 / 2O2
2.
1 / 2O2 1 / 2 N 2 NO
K 2( 3000K) 0.1222
38
X CO X O1 / 2
2
X CO
a
(4 a) / 2
X O2
1 / 2(1 a b)
(4 a) / 2
X CO2
1 a
(4 a) / 2
Substituting yields:
K1 0.3273
X CO X O1 / 2
2
X CO
a 1 a b
1 a 4 a
1/ 2
(1)
39
X NO
2b
(2)
b= 0.0675
d= 0.6535
e= 0.4663
40
41
(stoich)
(rich)
Mole fraction, Xi
(lean)
Temperature (K)
42
Note dissociation in the products will result in a lower AFT since dissociation
reactions are endothermic.
Again computer programs are used for these calculations:
http://www.wiley.com/college/mechs/ferguson356174/wave_s.html
Adiabatic Flame Temperature Applet
and STANJAN
43
Chemical Kinetics
First and Second Laws of thermodynamics are used to predict the final
equilibrium state of the products after the reaction is complete.
Chemical kinetics deals with how fast the reaction proceeds.
F F A A C C D D
How fast the fuel is consumed is of interest, the reaction rate is defined
as:
d[F ]
'''
dt
where [ F ] refers to the fuel concentration (kmol/m3 or kg/m3), negative sign
due to the fact that the fuel is consumed.
Global (or overall) reactions describe the initial and final states:
C8 H18 12.5(O2 3.76 N 2 ) 8CO2 9 H 2O 47 N 2
H 2 1 / 2O2 H 2O
44
Reaction Mechanism
In reality the reaction proceeds through elementary reactions in a chain
process known as chain reactions
The global hydrogen-oxygen reaction proceeds via the following elementary
reactions, collectively known as a reaction mechanism:
H2 M H H M
Chain initiation
H O 2 M HO 2 M
HO 2 H 2 H 2 O OH
Chain propagation
OH H 2 H 2 O H
H O 2 OH O
H 2 O OH H
Chain branching
H OH M H 2 O M
H H M H2 M
Chain termination
O O M O2 M
( M is any species present th at acts as a collision partner)
45
Radicals
Species such as H, O, OH and HO2 are called radicals.
Radicals have unpaired valence electrons which make them very reactive
and short lived, they try to partner with other radicals to form covalent bonds
In chain branching reactions there is a net production of radicals
Chain branching reactions lead to rapid production of radicals which causes
the overall reaction to proceed extremely fast explosively
The reaction comes to completion through chain termination reactions
where the radicals recombine to form final products.
46
products
47
j
n
d [ Ai ]
"
'
( i i )k [ A j ]
dt
j 1
'j
1'
2'
3'
n'
where [ A j ] [ A1 ] [ A2 ] [ A3 ] [ An ]
j 1
n
d [ Ai ] m "
'
( i ,l i ,l )kl [ A j ]
l 1
dt
j 1
'
j .l
48
d [ A1 ]
( 1" 1' )k[ A1 ] [ A2 ]
dt
d[H ]
(1 3)k[ H ]3 [ H 2 ]0 2k[ H ]3
dt
'
1
A1 = H
'
2
d [ A2 ]
( 2" 2' )k[ A2 ] [ A2 ]
dt
d[H 2 ]
(1 0)k[ H ]3 [ H 2 ]0 k [ H ]3
dt
'
1
A2 = H2
Recall n = 2
note k[H]3
'
2
1 d[H ] d[ H 2 ]
2 dt
dt
49
d[H 2 ]
E
k[ H ]3 AT b exp a [ H ]3
dt
RT
The values of a, b and Ea are tabulated for different reactions.
This expression indicates that molecular hydrogen is produced faster at
higher temperature and at a higher atomic hydrogen concentration.
50
Ea
n-1
Temperature range
(kJ/gmol)
(K)
51
2O3 3O2
k
1
O3 M
O O2 M
Important elementary
reactions include:
k2
3
O O3 k
O2 O2
k4
5
OOM
O2 M
k6
d [ Ai ]
( i",l i',l )kl [ A j ]
l 1
dt
j 1
m
O'''
3
d [O3 ]
k1[O3 ][ M ] k 2 [O][O2 ][ M ] k3 [O][O3 ] k 4 [O2 ]2
dt
52
A A B B C C D D
kb
d [ A]
k f [ A] [ B ] kb [C ] [ D]
dt
A
d [ A]
k f [ A] [ B ] kb [C ] [ D ] 0
dt
At equilibrium:
[C ] [ D]
kb [ A] [ B ]
kf
Note:
X CvC
X AvA
X DvD
X BvB
P
P
ref
k f [ A] [ B ] kb [C ] [ D]
Recall:
vC vD v A vB
nC
nC / V
RT
XC
[C ]
ntotal ntotal / V
P
[C ] [ D] R T
[ A]v [ B ]v Pref
vC
vD
53
vC vD v A vB
K
kb Pref
RT
kb
Pref
kf
vC vD v A vB
vC vD v A vB
54
Empirical correlations have been developed for the fuel reaction rate:
d [ Fuel ]
E
n
m
l
A exp
[ Fuel ] [O2 ] [ Inert]
dt
RT
where [ ] in units of gmol/cm3
R = 1.987 cal/gmolK
E typically 20 - 40 kcal/gmol
Note this is a correlation so n, m and l dont have to be integers, typically l= 0
55
G
N 2 O2 k
2 NO
O N 2 NO N
Ea 315 kJ/mol
(2)
N O2 NO O
Ea 26 kJ/mol
Forward reaction (1) is endothermic and due to the high Ea requires high
temperature (>1800K) to proceed and is very slow.
From above two reaction using basic arguments one can derive the following
expression for the initial NO reaction rate for the global reaction:
KPref
d [ NO]
2k f 1
[ N 2 ][O2 ]1/ 2
dt
RT
kG
56
Explosion Limits
H2-O2
P
Vacuum
T
time
Explosion Limits
If you repeat the experiment for different fill pressures and plot all the results on a
pressure-temperature curve one can define an explosion limit curve.
The shape of this limit curve can be explained by the temperature and pressure
dependencies of the H2-O2 elementary reactions.
1 atm
NO Explosion
Explosion Limits of
Stoichiometric H2-O2
Explosion
58
burned
Vb
b
Vu = Sl
unburned
Stationary flame
Vb-Sl
Sl
Vu = 0
u
Moving flame
60
Tu P
298K 1atm
(1 2.1Ydil )
where Ydil is the mass fraction of diluent, e.g., residual gas, and
Sl ,ref BM B2 ( M )
2.18 0.8( 1)
0.16 0.22( 1)
Fuel
Methanol
Propane
Isooctane
1.11
1.08
1.13
BM (cm/s)
36.92
34.22
26.32
B2 (cm/s)
-140.51
-138.65
-84.72
61
Structure of Flame
Vu = SL
u
Vb
b
[Fuel]
[O2]
d[F ]
Ea
[ F ]n [O2 ]m exp
dt
RT
Products
zone
[radicals]
Reaction
Zone
Flame
thickness
Pre-heat
Zone
Diffusion of heat
and radicals
62
Flame Velocity
The laminar burning velocity is measured relative to the unburned gas ahead
and the flame velocity Vf is measured relative to a fixed observer.
If the flame is propagating in a closed-ended tube the velocity measured is the
flame velocity and can be up to 8 times the burning velocity.
This is because the density of the products is lower than the fresh gas so a
flow is generated ahead of the flame
Vb=0
b
Vf
Vu
Vf
Vb=Vf
b
Moving flame
V f - V u= S l
u
Stationary flame
63
Turbulent Flames
Unlike the laminar burning velocity, the turbulent flame velocity is not a
property of the gas but instead it depends on the details of the flow.
The IC engine in-cylinder flow is always turbulent and the smallest eddies
(Kolmogorov scale) are typically larger than the laminar flame thickness (1 mm).
Under these conditions the flame is said to display a structure known as
wrinkled laminar flame.
A wrinkled laminar flame is characterized by a continuous flame sheet that is
distorted by the eddies passing through the flame.
The turbulent burning velocity depends on the turbulent intensity ut and can
be up to 30 times the laminar burning velocity
Sl
Laminar flame
St
Turbulent flame
S t / S l 1 a ut / S l
64
1 mm
Sl Sl c p
As a flame propagates through a duct heat is lost from the flame to the wall
Local quenching
67