3.

Combustion Chemistry
- For many kinetically controlled systems, the num-
ber of elementary reaction steps is so large that
simple analytical solutions are not possible.
- Most of the time, a large number of chemical
species are involved.
- Even in combustion of simple hydrocarbons, num-
ber of species involved is quite high.
- To illustrate how the fundamental principles of
chemical kinetics apply to real-world problems, we
will consider some examples.
3. Combustion Chemistry 1 AER 1304 LG
Hydrogen-Oxygen Reaction
The reaction between hydrogen and oxygen is a good
example of a multicomponent kinetic system. To de-
scribe the sysytem properly, we should consider eight
major species and at least 16 reactions.
- The overall reaction is:
2H
2
+ O
2
2H
2
O
This reaction is exothermic; but mixtures of
gaseous hydrogen and oxygen are quite stable at
atmospheric conditions. Any conceivable direct
reaction between the two gases is zero.
3. Combustion Chemistry 2 AER 1304 LG
- The reaction half-time at atmospheric conditions
has been estimated to be much larger than the age
of the universe.
- If the reaction is initiated by some free-radical
species, then the reaction proceeds very rapidly
and violently.
- The radicals are typically H and O atoms pro-
duced from the dissociation of H
2
and O
2
, re-
spectively.
- We will consider a simplified mechanism that rep-
resents the gross features of H
2
+ O
2
at low P.
3. Combustion Chemistry 3 AER 1304 LG
- Initiation
H
2
k
o
2H (H.0a)
O
2
k
o
2O (H.0b)
- Chain branching
O
2
+ H
k
2
OH + O (H.2)
H
2
+ O
k
3
OH + H (H.3)
- Chain propagation
3. Combustion Chemistry 4 AER 1304 LG
H
2
+ OH
k
1
H
2
O + H (H.1)
- Chain termination
H + wall
k
4
(1/2)H
2
(H.4)
H + O
2
+ M
k
5
HO
2
+ M (H.5)
- Initiation step is the dissociation of some amount
of molecular species by a spark, flame, electric
discharge, or some other means.
3. Combustion Chemistry 5 AER 1304 LG
- Bond energies:
O = O : 5.1 eV
HH : 4.5 eV
OH : 4.4 eV
- Reaction (2) is endothermic by 0.7 eV (about 70
kJ/mol) and progresses slowly.
- Reactions (3) and (1) are endothermic by 0.1 eV,
and these reactions are relatively fast.
- The OH and O radicals are therefore rapidly con-
sumed, and the principal chain carrier is H atoms.
3. Combustion Chemistry 6 AER 1304 LG
- We will find the rate equation for the free-radical
density n

, which is taken to be the same as that

for [H] atoms:
dn

dt
=
d[H]
dt
= k
o
[H
2
] k
2
[H][O
2
] + k
3
[O][H
2
] + k
1
[OH][H
2
]
k
4
[H] k
5
[H][O
2
][M] (3.1)
- For other free-radical species:
d[OH]
dt
= k
2
[H][O
2
] + k
3
[O][H
2
] k
1
[OH][H
2
]
(3.2)
3. Combustion Chemistry 7 AER 1304 LG
d[O]
dt
= k
o
[O
2
] + k
2
[H][O
2
] k
3
[O][H
2
] (3.3)
- Since [O] and [OH] are both much lower than
[H], we can assume that both of these species are
at steady-state:
d[OH]
dt
=
d[O]
dt
= 0 (3.4)
that yields
[O]
ss
=
k
o
[O
2
] + k
2
[H][O
2
]
k
3
[H
2
]
(3.5)
3. Combustion Chemistry 8 AER 1304 LG
and for [OH],
[OH]
ss
=
k
2
[H][O
2
] + k
3
[O][H
2
]
k
1
[H
2
]
(3.6)
Substituting for [O]
ss
[OH]
ss
=
2k
2
[H][O
2
] + k
o
[O
2
]
k
1
[H
2
]
(3.7)
- We substitute the steady-state values of [OH] and
[O] radicals in the rate equation for free-radical
density
3. Combustion Chemistry 9 AER 1304 LG
dn

dt
= k
o
[H
2
] k
2
[H][O
2
] +k
3
k
2
[H][O
2
] + k
o
[O
2
]
k
3
[H
2
]
[H
2
]
+k
1
[H
2
]
2k
2
[H][O
2
] + k
o
[O
2
]
k
1
[H
2
]
k
4
[H] k
5
[H][O
2
][M]
= k
o
([H
2
] + 2[O
2
])

w
o
+(2k
2
[O
2
]

f
k
4
k
5
[O
2
][M]

g
)n

(3.8)
so that
dn

dt
= w
o
+ (f g)n

(3.9)
3. Combustion Chemistry 10 AER 1304 LG
- f: chain branching
- g: chain termination
- Two classes of solutions are possible:
1. g > f: termination exceeds branching
2. g < f: branching exceeds termination
- Solution 1 implies that
k
4
> (2k
2
k
5
[M])[O
2
] (3.10)
so that g > f is assured at sufficiently low O
2
pressures.
3. Combustion Chemistry 11 AER 1304 LG
Time, t
F
r
e
e
-
r
a
d
i
c
a
l

d
e
n
s
i
t
y
,

n
*

o
/(g-f)
n* ~
o
t
3. Combustion Chemistry 12 AER 1304 LG
- The solution is then
n

=
w
o
g f
{1 e
(gf)t
} (3.11)
- At short times, n

increases almost linearly with

slope w
o
t and reaches a steady-state value of
n

ss
= w
o
/(g f) (3.12)
- At higher O
2
pressures g < f, then
n

=
w
o
f g
{e
(fg)t
1} (3.13)
3. Combustion Chemistry 13 AER 1304 LG
Time, t
F
r
e
e
-
r
a
d
i
c
a
l

d
e
n
s
i
t
y
,

n
*
3. Combustion Chemistry 14 AER 1304 LG
- In this case, the free-radical concentration in-
creases exponentially, and, since the overall rate
depends on the radical concentration, the reaction
velocity increases rapidly. This is usually termed
as an explosion.
- The hydrogen-oxygen reaction behaves quite dif-
ferently in different pressure regimes.
- It is possible to construct an explosion boundary
for the hydrogen-oxygen reaction as a function of
temperature and pressure.
3. Combustion Chemistry 15 AER 1304 LG
Total Pressure (H
2
+ O
2
)
T
o
t
a
l

R
a
t
e
P
1
* P
2
* P
3
*
I II III IV
Slow reaction
Chain-reaction
Explosion
Atmospheric flame
Thermal
Explosion
3. Combustion Chemistry 16 AER 1304 LG
- Region I: The reaction is wall-recombination lim-
ited, and proceeds to a steady-state.
- Region II: f begins to exceed g, the branched-
chain reaction takes over and explosion ensues.
- Region III: As the pressure is further increased,
the explosion is quenched and another regime of
steady-state is encountered.
In III, kinetics are dominated by relatively unreac-
tive HO
2
(hydroperoxyl) radicals. Other reactions,
in addition to those we considered above, are im-
portant and include the following:
3. Combustion Chemistry 17 AER 1304 LG
2HO
2
H
2
O
2
+ O
2
(H.6)
H
2
+ HO
2
H
2
O
2
+ H (H.7)
H + HO
2
2OH (H.8)
H + HO
2
H
2
+ O
2
(H.9)
H + HO
2
H
2
O + O (H.10)
H
2
O
2
+ M2OH + M (H.11)
H
2
O
2
+ H H
2
O + OH (H.12)
H
2
O
2
+ H H
2
+ O
2
(H.13)
H
2
O
2
+ OH H
2
O + HO
2
(H.14)
H + OH + MH
2
O + M (H.15)
H + H + MH
2
+ M (H.16)
3. Combustion Chemistry 18 AER 1304 LG
- Region IV: At a still high pressure, the amount of
heat liberated in the exothermic steps of the mech-
anism becomes larger than can be dissipated by
conduction and other thermal transport processes,
and the temperature rises. This, in turn increases
the rates of initiation and provides heat for en-
dothermic chain-branching reactions leading to
more heat release, resulting in a thermal explosion.
Experimentally observed (P T) boundaries of
the H
2
-O
2
reaction in a closed vessel is shown
below.
3. Combustion Chemistry 19 AER 1304 LG
3. Combustion Chemistry 20 AER 1304 LG
Carbon Monoxide Oxidation
Oxidation of CO is important in hydrocarbon com-
bustion.
From a very simplistic point-of-view, hydrocarbon
combustion (related to C content) can be charac-
terized as a two-step process:
- breakdown of fuel to CO.
- oxidation of CO to CO
2
.
CO oxidation is extremely slow in the absence of
small amounts of H
2
or H
2
O.
3. Combustion Chemistry 21 AER 1304 LG
If the H
2
O is the primary hydrogen-containing
species, the CO oxidation can be described by:
CO + O
2
CO
2
+ O (CO.1)
O + H
2
O OH + OH (CO.2)
CO + OH CO
2
+ H (CO.3)
H + O
2
OH + O (CO.4)
- (CO.1) is slow; not much contribution to CO
2
formation, but chain inititation reaction.
- (CO.3) is the actual CO oxidation step; also chain-
propagation step producing H atoms.
3. Combustion Chemistry 22 AER 1304 LG
- (CO.2) and (CO.4) are chain-branching reactions
producing OH, and OH and H, respectively.
- (CO.3) reaction is the key step in CO oxidation.
If H
2
is present, then following steps are involved:
O + H
2
OH + H (CO.5)
OH + H
2
H
2
O + H (CO.6)
CO + HO
2
CO
2
+ OH (CO.7)
- In the presence of H
2
, the entire H
2
-O
2
reaction
system should be included to describe CO oxida-
tion.
3. Combustion Chemistry 23 AER 1304 LG
Oxidation of Higher Paraffins
General Scheme:
Alkanes=Paraffins: saturated, straight chain or
branched-chain, single-bonded hydrocarbons.
General formula: C
n
H
2n+2
.
Generic oxidation discussion will be for n > 2.
Methane (and ethane) display some unique charac-
teristics not common with higher alkanes.
Overview of the key points of alkane oxidation.
3. Combustion Chemistry 24 AER 1304 LG
Three sequential processes:
I. Fuel is attacked by O and H; breaks down
to H
2
and olefins (double-bonded straight
hydrocarbons). H
2
oxidizes to H
2
O.
II. Unsaturated olefins form CO and H
2
. Almost
all H
2
converts to water.
III. CO burns to CO
2
releasing almost all of the
heat associated with combustion:
CO + OH CO
2
+ H (CO.3)
3. Combustion Chemistry 25 AER 1304 LG
These three processes can be further detailed as
(with the example of propane, C
3
H
8
):
Step#1. A C-C bond is broken in the original fuel
molecule. A C-C bond is weaker than an H-
C bond.
C
3
H
8
+ MC
2
H
5
+ CH
3
+ M (P.1)
Step#2. Two resulting hydrocarbon radicals break
down further to olefins: H-atom abstraction.
C
2
H
5
+ MC
2
H
4
+ H + M (P.2a)
CH
3
+ MCH
2
+ H + M (P.2b)
3. Combustion Chemistry 26 AER 1304 LG
Step#3. H atoms from Step#2 starts a radical pool:
H + O
2
O + OH (P.3)
Step#4. With the development of a radical pool, at-
tack on the fuel molecule intensifies.
C
3
H
8
+ OH C
3
H
7
+ H
2
O (P.4a)
C
3
H
8
+ H C
3
H
7
+ H
2
(P.4b)
C
3
H
8
+ O C
3
H
7
+ OH (P.4c)
3. Combustion Chemistry 27 AER 1304 LG
Step#5. Hydrocarbon radicals decay to olefins and H
atoms via H-atom abstraction.
C
3
H
7
+ MC
3
H
6
+ H + M (P.5)
This process obeys the -scission rule, which
states that C-C or C-H bond broken will be
the one that is one place removed from the
radical site.
C
3
H
6
+ H + M
C
3
H
7
+ M
C
2
H
4
+ CH
3
+ M
(P.6)
3. Combustion Chemistry 28 AER 1304 LG
3. Combustion Chemistry 29 AER 1304 LG
Step#6. Oxidation of olefins created in Steps#2 and
5 by O that produces formyl radicals (HCO)
and formaldehyde (H
2
CO).
C
3
H
6
+ O C
2
H
5
+ HCO (P.7a)
C
3
H
6
+ O C
2
H
4
+ H
2
CO (P.7b)
Step#7. Methyl radicals (CH
3
), formaldeydhe
(H
2
CO), and methylene (CH
2
) oxidize.
Step#8. Carbon monoxide oxidizes following the CO
mechanism discussed previously.
3. Combustion Chemistry 30 AER 1304 LG
Hierarchy in the reaction mechanism
describing alkane combustion.
3. Combustion Chemistry 31 AER 1304 LG
Global Mechanisms:
Global models do not capture all the features of
hydrocarbon combustion, but they may be useful
in simple engineering approximations as long as
their limitations are recognized.
A single-step expression:
C
x
H
y
+ (x + y/4)O
2
k
G
xCO
2
+ (y/2)H
2
O
(G.1)
d[C
x
H
y
]
dt
= Aexp[E
a
/(R
u
T)][C
x
H
y
]
m
[O
2
]
n
(G.2)
3. Combustion Chemistry 32 AER 1304 LG
A multi-step global mechanism:
C
n
H
2n+2
(n/2)C
2
H
4
+ H
2
(M.1)
C
2
H
4
+ O
2
2CO + 2H
2
(M.2)
CO + (1/2)O
2
CO
2
(M.3)
H
2
+ (1/2)O
2
H
2
O (M.4)
which assumes that the intermediate hydrocarbon
is ethylene (C
2
H
4
).
3. Combustion Chemistry 33 AER 1304 LG
Methane oxidation mechanism
3. Combustion Chemistry 34 AER 1304 LG
Nitrogen Oxide Kinetics
- Combustion products contain NO at levels of sev-
eral hundred to several thousand parts per million
(ppm) and NO
2
levels in tens of ppm.
- In the atmosphere, in the presence of ultraviolet
sunlight, an equilibrium is established:
NO
2
+ O
2
h

NO + O
3

ozone
3. Combustion Chemistry 35 AER 1304 LG
- Presence of certain hydrocarbons (e.g., unburned
hydrocarbons from combustion, methane from var-
ious sources) slowly unbalances the above reac-
tion.
- NO contributes to destruction of ozone in strato-
sphere.
- NO contributes to production of ground level
ozone.
- NO is involved in photochemical smog and haze.
3. Combustion Chemistry 36 AER 1304 LG
The main sources of nitrogen oxide, NO
x
, emissions
from combustion are:
- Thermal NO: oxidation of molecular nitrogen in
the postflame zone.
- Prompt NO: formation of NO in the flame zone
(Fenimore mechanism).
- N
2
O-intermediate mechanism.
- Fuel NO: oxidation of nitrogen-containing com-
pounds in the fuel.
Relative importance of these three are dependent on
the operating conditions and fuel. In most practical
combustion devices the thermal NO is the main source.
3. Combustion Chemistry 37 AER 1304 LG
The basic mechanism for thermal NO production
is given by six reactions known as
extended Zeldovich mechanism:
O + N
2
k
1f

k
1r
NO + N (N.1)
N + O
2
k
2f

k
2r
NO + O (N.2)
N + OH
k
3f

k
3r
NO + H (N.3)
3. Combustion Chemistry 38 AER 1304 LG
- The contribution of reaction 3 is small for lean
mixtures, but for rich mixtures it should be con-
sidered. Forward reaction 1 controls the system,
but it is slow at low temperatures (high activation
energy). Thus it is effective in post-flame zone
where temperature is high and the time is avail-
able.
- Concentrations of 1000 to 4000 ppm are typically
observed in uncontrolled combustion systems.
- From reactions 1-3, the rate of formation of ther-
mal NO can be calculated:
3. Combustion Chemistry 39 AER 1304 LG
d[NO]
dt
= k
1f
[O][N
2
] k
1r
[NO][N] + k
2f
[N][O
2
]
k
2r
[NO][O] + k
3f
[N][OH] k
3r
[NO][H] (3.14)
- To calculate the NO formation rate, we need the
concentrations of O, N, OH, and H.
- In detailed calculations, these are computed using
detailed kinetic mechanisms for the fuel used.
- For very approximate calculations, these may be
assumed to be in chemical equilibrium.
3. Combustion Chemistry 40 AER 1304 LG
- At moderately high temperatures N does not stay
at thermodynamic equilibrium. A better approxi-
mation could be to assume N to be at steady-state.
- From reactions 1-3, we have
d[N]
dt
= k
1f
[O][N
2
] k
1r
[NO][N] k
2f
[N][O
2
]
+k
2r
[NO][O] k
3f
[N][OH] + k
3r
[NO][H] = 0
[N]
ss
=
k
1f
[O][N
2
] + k
2r
[NO][O] + k
3r
[NO][H]
k
1r
[NO] + k
2f
[O
2
] + k
3f
[OH]
(3.15)
3. Combustion Chemistry 41 AER 1304 LG
- The reaction rate constants, in [m
3
/ kmol s], for
1-3 are as follows:
k
1f
= 1.8 10
11
exp(38, 370/T)
k
1r
= 3.8 10
10
exp(425/T)
k
2f
= 1.8 10
7
T exp(4680/T)
k
2r
= 3.8 10
6
T exp(20, 820/T)
k
3f
= 7.1 10
10
exp(450/T)
k
3r
= 1.7 10
11
exp(24, 560/T)
(5.16)
3. Combustion Chemistry 42 AER 1304 LG
N
2
O-intermediate mechanism is important in very-
lean combustion ( < 0.8). This mechanism can
be represented by:
O + N
2
+ M

N
2
O + M (N.4)
H + N
2
O

NO + NH (N.5)
O + N
2
O

NO + NO (N.6)
- This mechanism is important in NO control strate-
gies in lean-premixed gas turbine combustion ap-
plications.
3. Combustion Chemistry 43 AER 1304 LG
It has been shown that some NO is rapidly pro-
duced in the flame zone long before there would
be time to form NO by the thermal mechanism.
This is also known as the Fenimore mechanism:
- The general scheme is that hydrocarbon radicals
form CN and HCN
CH + N
2

HCN + N (N.7)
C + N
2

CN + N (N.8)
3. Combustion Chemistry 44 AER 1304 LG
- The conversion of hydrogen cyanide, HCN, to
form NO is as follows
HCN + O

NCO + H (N.9)
NCO + H

NH + CO (N.10)
NH + H

N + H
2
(N.11)
N + OH

NO + H (N.3)
- For equivalence ratios higher than 1.2, chemistry
becomes more complex and it couples with the
thermal mechanism.
3. Combustion Chemistry 45 AER 1304 LG