Active parameters are selected from uncertainty impact ranking as follows.
Number |
Reaction |
Uncertainty Factor f |
1 |
H+O2<=>O+OH |
1.15 |
2 |
O+H2<=>H+OH (low T) |
1.6 |
3 |
O+H2<=>H+OH (high T) |
1.6 |
4 |
OH+H2<=>H+H2O |
1.2 |
5 |
2OH<=>O+H2O |
1.4 |
6 |
H2+M<=>2H+M(N2) |
3 |
6 |
H2+M<=>2H+M(H2) |
3 |
6 |
H2+M<=>2H+M(H2O) |
3 |
6 |
H2+M<=>2H+M(CO) |
3 |
6 |
H2+M<=>2H+M(CO2) |
3 |
7 |
H2+AR<=>2H+AR |
2 |
12 |
O+H+M<=>OH+M(N2) |
5 |
12 |
O+H+M<=>OH+M(H2O) |
5 |
12 |
O+H+M<=>OH+M(CO) |
5 |
12 |
O+H+M<=>OH+M(CO2) |
5 |
13 |
H2O+M<=>H+OH+M(AR) |
3.2 |
13 |
H2O+M<=>H+OH+M(HE) |
3.2 |
13 |
H2O+M<=>H+OH+M(N2) |
3.2 |
13 |
H2O+M<=>H+OH+M(H2) |
3.2 |
13 |
H2O+M<=>H+OH+M(CO) |
3.2 |
13 |
H2O+M<=>H+OH+M(CO2) |
3.2 |
14 |
2H2O<=>H+OH+H2O |
3.2 |
15 |
H+O2(+M)<=>HO2(+M) (k∞) |
2 |
15 |
H+O2(+M)<=>HO2(+M)(AR) |
2 |
15 |
H+O2(+M)<=>HO2(+M)(HE) |
2 |
15 |
H+O2(+M)<=>HO2(+M)(N2) |
2 |
15 |
H+O2(+M)<=>HO2(+M)(H2) |
2 |
15 |
H+O2(+M)<=>HO2(+M)(O2) |
2 |
15 |
H+O2(+M)<=>HO2(+M)(H2O) |
2 |
15 |
H+O2(+M)<=>HO2(+M)(CO) |
2 |
15 |
H+O2(+M)<=>HO2(+M)(CO2) |
2 |
16 |
HO2+H<=>H2+O2 |
2 |
17 |
HO2+H<=>2OH |
2 |
18 |
HO2+H<=>O+H2O |
3 |
19 |
HO2+O<=>OH+O2 |
3 |
20 |
HO2+OH<=>H2O+O2 |
1.6 |
21 |
HO2+OH<=>H2O+O2 |
1.35 |
22 |
2HO2<=>H2O2+O2 |
1.5 |
23 |
2HO2<=>H2O2+O2 |
2 |
24 |
H2O2(+M)<=>2OH(+M) (k∞) |
2.5 |
24 |
H2O2(+M)<=>2OH(+M)(AR) |
2.5 |
24 |
H2O2(+M)<=>2OH(+M)(N2) |
2.5 |
24 |
H2O2(+M)<=>2OH(+M)(H2) |
2.5 |
24 |
H2O2(+M)<=>2OH(+M)(H2O) |
2.5 |
24 |
H2O2(+M)<=>2OH(+M)(H2O2) |
2.5 |
24 |
H2O2(+M)<=>2OH(+M)(CH2O) |
2.5 |
25 |
H2O2+H<=>OH+H2O |
2 |
26 |
H2O2+H<=>HO2+H2 |
2 |
27 |
H2O2+O<=>OH+HO2 |
3 |
28 |
H2O2+OH<=>H2O+HO2 |
2 |
29 |
H2O2+OH<=>H2O+HO2 |
1.3 |
30 |
CO+O(+M)<=>CO2(+M) (k∞) |
10 |
31 |
CO+O2<=>O+CO2 |
10 |
32 |
CO+OH<=>H+CO2 (high T) |
1.2 |
33 |
CO+OH<=>H+CO2 (low T) |
1.5 |
35 |
HCO+M<=>H+CO+M(AR) |
1.7 |
35 |
HCO+M<=>H+CO+M(HE) |
1.7 |
35 |
HCO+M<=>H+CO+M(N2) |
1.7 |
35 |
HCO+M<=>H+CO+M(H2) |
1.7 |
35 |
HCO+M<=>H+CO+M(O2) |
1.7 |
35 |
HCO+M<=>H+CO+M(H2O) |
1.7 |
35 |
HCO+M<=>H+CO+M(CO) |
1.7 |
35 |
HCO+M<=>H+CO+M(CH4) |
1.7 |
35 |
HCO+M<=>H+CO+M(CH2O) |
1.7 |
36 |
HCO+H<=>H2+CO |
2.5 |
38 |
HCO+O<=>H+CO2 |
2 |
39 |
HCO+OH<=>H2O+CO |
2 |
40 |
HCO+O2<=>HO2+CO |
2 |
43 |
CH+H<=>C+H2 |
1.5 |
46 |
CH+H2<=>H+CH2 |
3 |
47 |
CH+H2(+M)<=>CH3(+M)(AR) |
2 |
50 |
CH+O2<=>CO2+H |
1.6 |
51 |
CH+O2<=>CO+OH |
1.6 |
52 |
CH+O2=>O+H+CO |
1.6 |
57 |
CH2+OH<=>H+CH2O |
3 |
60 |
CH2+H2<=>H+CH3 |
9 |
61 |
CH2+O2=>OH+H+CO |
2 |
62 |
CH2+O2=>2H+CO2 |
2 |
63 |
CH2+O2<=>O+CH2O |
2 |
64 |
CH2+O2<=>H2+CO2 |
2 |
76 |
CH2(S)+H2<=>CH3+H |
2 |
85 |
HCO+H(+M)<=>CH2O(+M) (k∞) |
3 |
85 |
HCO+H(+M)<=>CH2O(+M)(AR) |
3 |
85 |
HCO+H(+M)<=>CH2O(+M)(CH2O) |
3 |
86 |
CH2O(+M)<=>H2+CO(+M)(AR) |
2.5 |
87 |
CH2O+H<=>HCO+H2 |
2 |
88 |
CH2O+O<=>OH+HCO |
1.6 |
89 |
CH2O+OH<=>HCO+H2O |
2 |
90 |
CH2O+O2<=>HO2+HCO |
3 |
91 |
CH2O+HO2<=>HCO+H2O2 |
3 |
97 |
CH3+H(+M)<=>CH4(+M) (k∞) |
2 |
97 |
CH3+H(+M)<=>CH4(+M)(AR) |
3 |
97 |
CH3+H(+M)<=>CH4(+M)(HE) |
3 |
97 |
CH3+H(+M)<=>CH4(+M)(N2) |
3 |
97 |
CH3+H(+M)<=>CH4(+M)(O2) |
3 |
97 |
CH3+H(+M)<=>CH4(+M)(H2O) |
3 |
97 |
CH3+H(+M)<=>CH4(+M)(CO) |
3 |
98 |
CH3+O<=>H+CH2O |
1.4 |
99 |
CH3+O=>H+H2+CO |
1.4 |
101 |
CH3+OH<=>CH2+H2O |
2 |
102 |
CH3+OH<=>CH2(S)+H2O |
3 |
103 |
CH3+OH<=>H2+CH2O |
3 |
104 |
CH3+HO2<=>O2+CH4 |
3 |
105 |
CH3+HO2<=>OH+CH3O |
3 |
106 |
CH3+O2<=>O+CH3O |
2 |
107 |
CH3+O2<=>OH+CH2O |
3 |
109 |
CH3+CH<=>H+C2H3 |
10 |
110 |
CH3+CH2<=>H+C2H4 |
3 |
112 |
2CH3(+M)<=>C2H6(+M) (k∞) |
2 |
112 |
2CH3(+M)<=>C2H6(+M)(AR) |
2 |
112 |
2CH3(+M)<=>C2H6(+M)(O2) |
2 |
112 |
2CH3(+M)<=>C2H6(+M)(CH4) |
2 |
113 |
2CH3<=>H+C2H5 |
2 |
115 |
CH3+CH2O<=>HCO+CH4 |
2 |
127 |
CH2OH(+M)<=>H+CH2O(+M)(AR) |
2 |
127 |
CH2OH(+M)<=>H+CH2O(+M)(H2O) |
2 |
130 |
CH2OH+H<=>OH+CH3 |
2.5 |
134 |
CH2OH+O2<=>HO2+CH2O |
2 |
136 |
CH4+H<=>CH3+H2 |
1.5 |
137 |
CH4+O<=>OH+CH3 |
1.4 |
138 |
CH4+OH<=>CH3+H2O |
1.2 |
139 |
CH4+HO2<=>CH3+H2O2 |
2.5 |
141 |
CH4+CH2<=>2CH3 |
2 |
142 |
CH4+CH2(S)<=>2CH3 |
1.4 |
172 |
HCCO+O2<=>OH+2CO |
5 |
176 |
C2H2(+M)<=>H2CC(+M)(AR) |
3 |
178 |
C2H2+O<=>H+HCCO |
2 |
179 |
C2H2+O<=>CO+CH2 |
3.2 |
185 |
H2CC+O2<=>2HCO |
5 |
188 |
CH2CO+H<=>CH3+CO |
3 |
199 |
C2H3+H<=>H2CC+H2 |
4 |
204 |
C2H3+O2<=>HCO+CH2O |
2 |
205 |
C2H3+O2<=>CH2CHO+O |
3 |
237 |
C2H4(+M)<=>H2+H2CC(+M) (k∞) |
2 |
237 |
C2H4(+M)<=>H2+H2CC(+M)(AR) |
2 |
237 |
C2H4(+M)<=>H2+H2CC(+M)(CH4) |
2 |
238 |
C2H4+H(+M)<=>C2H5(+M) (k∞) |
2 |
238 |
C2H4+H(+M)<=>C2H5(+M)(N2) |
2 |
238 |
C2H4+H(+M)<=>C2H5(+M)(H2O) |
2 |
239 |
C2H4+H<=>C2H3+H2 |
2.5 |
240 |
C2H4+O<=>CH3+HCO |
2 |
243 |
C2H4+OH<=>C2H3+H2O |
2 |
249 |
C2H5+H(+M)<=>C2H6(+M)(AR) |
2 |
254 |
C2H5+O2<=>HO2+C2H4 |
2 |
258 |
C2H6+H<=>C2H5+H2 |
1.4 |
259 |
C2H6+O<=>OH+C2H5 |
2 |
260 |
C2H6+OH<=>C2H5+H2O |
1.6 |
261 |
C2H6+CH<=>CH3+C2H4 |
3 |
264 |
C2H6+CH3<=>C2H5+CH4 |
1.5 |
999 |
flw_1a [OH]0 (nominal: 100 ppm) |
10 |
999 |
flw_2a [OH]0 (nominal: 100 ppm) |
10 |
999 |
flw_3a [OH]0 (nominal: 10 ppm) |
2 |
999 |
flw_4a [OH]0 (nominal: 40 ppm) |
10 |
Special treatment is required for unimolecular reactions. In active parameter analysis, absolute low-pressure limit reaction rates with each collider was assumed to have the same uncertainty factor as the base rate coefficient (usually with N2 or Ar). In the optimization, however, third-body efficiencies relative to the base collider are considered as independent variables within a reasonable range. For the H+O2+M reaction, th ranges of relative third-body efficiencies are (expressed in the nomalized rate variable) He: ±0.3; Ar: ±0.2; O2: ±0.3; H2O: ±7; CO2: ±1.4; H2: ±1. For other, generic relative efficiencies, the ranges are: Ar, He: -0.2/+0.3; O2: ±0.2; CO: ±0.5; H2O ±3; CH4, CO2: ±1; H2: ±30%. Uncertainty factors of third body efficiencies are obtained by averaging the upper and lower bounds mentioned above.