Methane Combustion

Complex meihone combusiion mechonism (GRl Mech 2.,l I

) [1
01
Forward Rate Coefficient"
Reaction
159
ipecies,
. More
in
Ref.
-H
bond
or
exam-
ssentialiY
lhed
and'
,n kinetics
:iod
1970-
tary
steps'
rch
groups
nechanism
rtimization
rie
on
the
L Table
5'3'
3Se
steps
we
h 2.11),
we
)w-tempera-
A detailed
1owever,
for
e in a homo-
eactor
elimi-
as
would
be
,n dioxide
at a
/ represents
an
t sPecies
at the
3actant
specles
nding
reaction
{tives a
vlsual
p'u,t-r.
*ftitt
tt-t"
'the
reactant'
C-H-O Reactions
Tqble 5.3
6
1
gb
gb
t0
ll
12
t3
l4
l5
t6
t7
18
t9
20
21
22
23
24
25
26
21
28
29
30
O+O+M*O:*M
O+H+M+OH*M
O+H2*H+OH
o+Ho2-OH*O:
O+H2O2+oH*Hoz
O+CH-H-FCO
O+CH:+H+HCO
O+CH2(S)
-H:fCo
O+CH2(S)*H+HCO
O+CH3-H*CH:o
O+CH1-OH*CHr
o+Co*M-66r*t
O+HCO+OH+CO
O+HCO*H+CO2
O+CH:O*OH+HCO
O+CH:OH+OH{CH2O
O + CH:O
-
OH 1CH2O
O+CHTOH+OH*CH2OH
O+CH3OH*OH*CH:O
O+C:H+CH+CO
O+C2H2-H+HCCO
O+CrH2*OH*CzH
O+C2H2-CO+CHr
O*C:H3-H+CH2CO
O*C2Ha-CH:*HCO
O*C:Hs+CHr*CH:O
O*C2H6*OH*CzHs
O+HCCO+H+CO+CO
O+CH2CO-OH+HCCO
O+CH:CO+CH:*CO:
1.20E + l7
5.00E + l7
5.00E + 04
2.00E + l3
9.63E + 06
5.70E + l3
8.00E + 13
I .50E + l3
I .50E + 13
8.43E + l3
1.02E + 09
6.02E + 14
3.00E + 13
00E + 13
90E + 13
00E + 13
008 + l3
3.88E + 05
1.30E + 05
5.00E + t3
1.02E + 07
4.608 + l9
1..02E + 07
3.00E + l3
1S2E + 07
1.328 + 14
8.98E + 07
1.00E + l4
1.00E + 13
l.t5E+ t2
2.508 + t2
1.00E + 14
2.80E + l8
3.00E + 20
9.38E + l8
3.758 + 20
1.008 + t7
8.30E + 13
1 .00E + 18
9.00E + 16
6.008 + 19
5.508 + 20
2.208 + 22
3.978 + 12
2.80E + l3
1.348 + 14
,t.0
0.0
-
1.0 0.0
2.67 6,290
0.0 0.0
2.0 4,000
0.0 0.0
0.0 0.0
0.0 0.0
0.0 0.0
0.0 0.0
1.5 8,600
0.0 3,000
0.0 0.0
0.0 0.0
0.0 3,540
0.0 0.0
0.0 0.0
2.5 3, 100
2.5 5,000
0.0 0.0
2.0 I,900
|.41 28,950
2.0 I,900
0.0 0.0
1.83 220
0.0 0.0
t.92 5,690
0.0 0.0
0.0 8,000
0.0 I,350
0.0 47,800
0.0 40.000
-0.86
0.0
-1.72
0.0
-0.76
0.0
-1.72
0.0
-0.8
0.0
0.0 14,4t3
-
1.0 0.0
-0.6
0.0
-1.25
0.0
-2.0
0.0
-2.0
0.0
0.0 67 |
0.0 1,068
0.0 635
l1 02*CO-O+CO2
l2 02 * CH:O * HO: * HCO
l3 H+O:*M+HO:*M
14 H+O:*O:+HO:*O:
35 H+O:*H:O+HOz*H:O
36 H+Oz*N:*HOr*N:
37 H+O1 *Ar*HO:*Ar
l8 H+O:*O+OH
19 H+H+M+Hu*M
40 H+H+Hz*Hz*H:
11 H+H+H:O*H:*H:O
42 H+H+COz-H:*CO:
43 H+OH+M-H:O*M
14 H+HO2+O+H:O
45 H+HO2+02 1P1,
lb
H I HO2
.OH
OH
Methane
Combustion
155
Toble
5.3 (coniinued)
Forward Rate Coefficientu
-4,+0
,4,710
l:).0
0.0
0.0
0.0
20.000
48,000
110
800
I 26,600
4.9t30
1"980
16.600
1 1.370
6,400
9.000
1.900
400
46.020
20.400
71.000
65.000
0.0
0.0
0.0
0.0
0.0
1.270
164
580
1.210
160
580
18.800
2l .750
0.0
0.0
0.0
0.0
0.0
8.500
1.50E
+ 08
2.20E
+ 06
2.25E
+ 07
1.05E
+ 05
4.658
+ 12
1.55E
+ l2
1.18E
+ l6
2.10E+
l5
2.708
+ 1l
1.708
+ t4
2.00E
+ 07
2.35E
+ 13
6.r0E+ 14
3.708
+ 12
5.40E
+ 05
5.00E
+ 07
9.40E + 06
N-Containing
Reactions (
continued
)
263
HNCO+O*HNO*CO
264 HNCO+O*NCO+OH
265 HNCO+H+NHr+CO
266
HNCO+"*Hz+NCO
261 HNCO
+ OH *
N6g
1 1116
268 HNCO
+ OH +
Nfl,
166,
269 HNCO+M+NH+Co+M
210 HCNO+H*H+HNCO
2Tl HCNO+H*OH+HCN
272 HCNO+H*NHz*Co
|.57 44.000
2.tl
I 1,400
1.7
3,800
2.5
13.300
0.0 6,850
0.0
6,850
0.0 84,720
-0.69
2.850
0. 18
2,120
-0.75
2,890
2.0
2,000
0.0
0.0
-0.31
290
0.15
-90
273
11t
215
2T6
2TT
279
HOCN+H+H*HNCo
HCCO+NO+fif\Q16C)
CH:*N*H:CN+H
CH:+N-HCN*H:
NH:*H*NH:*H:
NH:*OH-NH:*HrO
NH:*O+NH:*OH
a1
t.6
t.94
9,91 5
955
6,460
oThe
forword roie coefficienr k: ATbexp(-ErRr).
R is fhe universor gos
consronl, r is ihe remperoture
in K.
Ihe units of A involve gmol/cm3
ond s, ond.ihose of E, cqllgmol.
"CH2(S) designotes the singlet s.tote of CH2.
From Fig. 5.4, we see a linear progressiotl
of CH4 to CO2, together
with
several side loops originating
from the methyl (cH3)
radical.lheli.rear
pro-
gression,
or backbone,
starts with an attack on the cHa molecule
by oH, o,
and H radicals
to produce
the methyl radical;
the methyl radical then combines
with an oxygen
atom to form formaldehyde
(cHzo);
the formaldehyde,
in
turn,
is attacked
by oH, H, and o radicals
to produce
the formyl
radical
(HCo);
the formal radical
is converted
to co by a trio of reactitns;
and,
finally,
co is converted
to co2, primarily
by reaction
with oH, as discussed
earlier.
Molecular
structure
diagrams
illuminate
the elegance
or inls sequence
of elementary
reactions
to explain,
in part,
the oxidation
of methane.
Drawing
such is left as an exercise for the reader.
In addition
to the direct pathway
from the methyl radical
to formaldehyde
(cH:
* o
-+
cH2o
+
H), the cH2 radicals
also react to form cH2 radicals in
two possible
electronic
configurations.
The singlet
electronic
stat! of cH2 is
designated
cH2(s) and should not be confused
with similar
notatio'
used to
indicate
a solid. There is also a side loop whereby
cH3 is first converted
to
cH20H,
which, in turn, is converted
to CH2o. ottrer tess important pathways
complete-the
mechanism.
Those pathways
with reaction
rates less ,rrun t toli
gmol/cm3-s
are not shown in Fie. 5.4.