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Revision 2.2 - (show annotations) (download)
Mon Jan 26 00:03:15 2015 UTC (9 years, 2 months ago) by gblanqu
Branch: MAIN
Changes since 2.1: +522 -428 lines
Chemistry submodels
- Completely revised CH* and OH* chemistry.  Better validated with C1 and C2 chemistry.
- C4H2 (mostly) reverted back to Hidaka.  Still requires a lot of work/improvements.
- Completely revised C4H6 chemistry.  Added two isomers (S-C4H6/D-C4H6) as in Laskin/Wang.  Inclusion of recent data.  Certain reactions revised based on C3Hx chemistry.

Reactions
- CH2O/CH3O decomposiiton moved around
- HCCO+O: systems revised
- C2H3+O2: revised rates/products with multiple (and consistent) recent exp data
- CH3CHO: completely revised based on CH2O and using recent QC results
- C2H2+CH: added reaction
- C4H8+H: reactions added from exp data
- A1C2H4+CH3O2: removed.

Rates
- T-CH2+H->CH3 : Ai reduced to collision limit
- CH2O decomposition revised to enforce experimental k at 1atm
- CH2O+H/OH: revised with exp data
- CH2O+CH: reduced to collision limit
- C2H2+H: typo for low P rate (missing third body efficiency)
- C2H4+M: typo for low P rate (missing third body efficiency)
- C2H4+H: typo for low P rate (missing third body efficiency)
- C2H4+H: revised with more recent (and more complete) exp data
- C3H2O+X: revised based on CH3CHO
- A-C3H4+CH3: revised based on C2H4+CH3
- C2H3CHO+X: revised based on CH3CHO
- C3H6+CH3: revised based on C2H4+CH3
- CnH2n decomp revised from exp data
- A1CHO+X: revised using CH3CHO
- A1C2H4+O2: revised with recent data
- A1CH3CHO+X: revised from CH3CHO
- A1CHOCHO+X: revised from CH3CHO
- A2CHO+X: revised from CH3CHO

Products
- HCCO+OH: products changed to ensure chain propagation
- C2H3+O: direct decomposition after collision
- C3H2+O: direct decomposition after collision
- A-C3H4+O: revised products based on recent exp data.  Now, it is chain breaking.
- P-C3H4+O: revised products (and rates) based on recent exp data.
- C3H6+O: revised products (and rates) based on recent exp data.
- A1C2H2+O2: revised based on C2H3+O2
1 Let allowed atoms be C, H, O, N, AR.
2 Let additional species be N2.
3 Let temperature exponent be n_k.
4 Let order of reaction be n.
5 Let units for A be [ cm^(3(n-1)) / ( s * mole^(n-1) * K^n_k ) ].
6 Let units for E be [ kJ / mole ].
7 Let symbol for soot be SOOT.
8
9
10 #=========================================================================#
11 # #
12 # "An Improved H2/O2 Mechanism #
13 # based on Recent Shock Tube/Laser Absorption Measurements" #
14 # Hong, Davidson, Hanson, Combust. Flame (2011) #
15 # #
16 #=========================================================================#
17
18
19 # Hydrogen/oxygen
20 # ---------------
21
22 1f: H + O2 -> O + OH { A = 1.04E+14 n = .00 E = 63.96 }
23 2f: O + H2 -> H + OH { A = 3.82E+12 n = .00 E = 33.25 }
24 3f: O + H2 -> H + OH { A = 8.79E+14 n = .00 E = 80.21 }
25 4f: OH + H2 -> H + H2O { A = 2.17E+08 n = 1.52 E = 14.46 }
26 5f: OH + OH -> O + H2O { A = 3.57E+04 n = 2.40 E = -8.83 }
27
28 # Davis et al. 2005
29 6f: 2 H + M1 -> H2 + M1 { A = 1.78E+18 n = -1.00 E = .00 }
30 7f: 2 H + H2 -> H2 + H2 { A = 9.00E+16 n = -0.60 E = .00 }
31 8f: 2 H + H2O -> H2 + H2O { A = 5.62E+19 n = -1.25 E = .00 }
32 9f: 2 H + CO2 -> H2 + CO2 { A = 5.50E+20 n = -2.00 E = .00 }
33
34 10f: O + H + M2 -> OH + M2 { A = 4.71E+18 n = -1.00 E = .00 }
35 11f: O + O + M3 -> O2 + M3 { A = 6.16E+15 n = -0.50 E = .00 }
36 12f: O + O + AR -> O2 + AR { A = 1.89E+13 n = .00 E = -7.48 }
37
38 # All rates recombined into a single
39 # Similar to Davis et al. 2005
40 # Collider efficiency evaluated at 1200K
41 13f: H + O2 + M4 -> HO2 + M4 { Ai= 5.59E+13 ni= 0.20 Ei= .00
42 A = 2.65E+19 n = -1.30 E = .00
43 fca = 0.3 fcta = 1.0E-10
44 fcb = 0.7 fctb = 1.0E+10
45 fcc = 1.0 fctc = 1.0E+10 }
46
47 14f: H2O + M5 -> OH + H + M5 { A = 6.06E+27 n = -3.31 E = 505.30 }
48 15f: H2O + H2O -> OH + H + H2O { A = 1.00E+26 n = -2.44 E = 502.75 }
49
50
51 # Hydroperoxy radical
52 # -------------------
53
54 16f: HO2 + H -> H2 + O2 { A = 3.66E+06 n = 2.09 E = -6.07 }
55 17f: HO2 + H -> O + H2O { A = 1.45E+12 n = .00 E = .00 }
56 18f: HO2 + H -> OH + OH { A = 7.08E+13 n = .00 E = 1.26 }
57 19f: HO2 + O -> OH + O2 { A = 1.63E+13 n = .00 E = -1.86 }
58
59 20f: HO2 + OH -> H2O + O2 { A = 2.89E+13 n = .00 E = -2.09 }
60 21f: HO2 + HO2 -> H2O2 + O2 { A = 1.30E+11 n = .00 E = -6.71 }
61 22f: HO2 + HO2 -> H2O2 + O2 { A = 4.20E+14 n = .00 E = 50.12 }
62
63
64 # Hydrogen peroxide
65 # -----------------
66
67 # Low P from Hong et al. 2011 - refitted
68 # Rest from Davis et al. 2005
69 23f: 2 OH + M6 -> H2O2 + M6 { A = 2.73E+19 n = -1.50 E = -9.59
70 Ai= 1.11E+14 ni= -0.37 Ei= .00
71 fcA = 0.2654 fctA = 94
72 fcb = 0.7346 fctb = 1756
73 fcc = 1.0 fctc = 5182 }
74
75 24f: H2O2 + H -> H2O + OH { A = 1.02E+13 n = .00 E = 14.97 }
76 25f: H2O2 + H -> HO2 + H2 { A = 1.21E+07 n = 2.00 E = 21.76 }
77 26f: H2O2 + O -> HO2 + OH { A = 8.43E+11 n = .00 E = 16.61 }
78 27f: H2O2 + OH -> HO2 + H2O { A = 1.74E+12 n = .00 E = 1.33 }
79 28f: H2O2 + OH -> HO2 + H2O { A = 7.59E+13 n = .00 E = 29.77 }
80
81
82
83 #=========================================================================#
84 # #
85 # "An optimized kinetic model of H2/CO combustion" #
86 # Davis, Joshi, Wang, and Egolfopoulos #
87 # Proc. Comb. Inst. 30 (2005) 1283-1292 #
88 # #
89 #=========================================================================#
90
91
92 # Carbon oxides
93 # -------------
94
95 30f: CO + O + M7 -> CO2 + M7 { A = 1.17E+24 n = -2.79 E = 17.54
96 Ai= 1.36E+10 ni= .00 Ei= 9.97
97 fcc = 1.0 fctc = 0.0 }
98 31f: CO + OH -> CO2 + H { A = 8.00E+11 n = 0.14 E = 30.76 }
99 32f: CO + OH -> CO2 + H { A = 8.78E+10 n = 0.03 E = -0.07 }
100 33f: CO + O2 -> CO2 + O { A = 1.12E+12 n = .00 E = 199.58 }
101 34f: CO + HO2 -> CO2 + OH { A = 3.01E+13 n = .00 E = 96.23 }
102
103 35f: HCO + M8 -> CO + H + M8 { A = 1.87E+17 n = -1.00 E = 71.13 }
104 36f: HCO + H2O -> CO + H + H2O { A = 2.24E+18 n = -1.00 E = 71.13 }
105
106 37f: HCO + H -> CO + H2 { A = 1.20E+14 n = .00 E = .00 }
107 38f: HCO + O -> CO + OH { A = 3.00E+13 n = .00 E = .00 }
108 39f: HCO + OH -> CO + H2O { A = 3.02E+13 n = .00 E = .00 }
109
110 40f: HCO + O -> CO2 + H { A = 3.00E+13 n = .00 E = .00 }
111
112 # New fit to experimental data
113 # Colbergs & Friedrichs 2006
114 41f: HCO + O2 -> CO + HO2 { A = 5.31E+10 n = 0.69 E = -0.52 }
115
116
117
118 #=========================================================================#
119 # #
120 # Kinetics of Excited states compiled mostly from #
121 # Kathrotia, Fikri, Bozkurt, Hartmann, Riedel, Schulz - Comb. Flame 2010 #
122 # Bozkurt, Fiki, Schulz - Appl Phys B (2012) #
123 # (some rates reduced to collison limit) #
124 # #
125 #=========================================================================#
126
127
128 # Excited OH*
129 # -----------
130
131 # Reduced by 2 to match abs values
132 E01f: O + H + M10 -> S-OH + M10 { A = 3.00E+12 n = .00 E = 25.00 }
133 E02f: CH + O2 -> S-OH + CO { A = 8.00E+10 n = .00 E = .00 }
134
135 E03f: S-OH -> OH { A = 1.45E+06 n = .00 E = .00 }
136 E04f: S-OH + AR -> OH + AR { A = 1.69E+12 n = .00 E = 17.32 }
137 E05f: S-OH + N2 -> OH + N2 { A = 1.08E+11 n = 0.50 E = -5.19 }
138 E06f: S-OH + O2 -> OH + O2 { A = 2.10E+12 n = 0.50 E = -2.02 }
139 E07f: S-OH + H2O -> OH + H2O { A = 1.55E+12 n = 0.50 E = -3.61 }
140 E08f: S-OH + CO -> OH + CO { A = 2.28E+12 n = 0.50 E = -3.30 }
141 E09f: S-OH + CO2 -> OH + CO2 { A = 1.61E+12 n = 0.50 E = -4.06 }
142
143
144 # Excited CH*
145 # -----------
146
147 E11f: C + H + M0 -> S-CH + M0 { A = 3.63E+13 n = .00 E = .00 }
148
149 # Devreindt, Peeters et al. 1997
150 E12f: C2H + O -> S-CH + CO { A = 1.44E+13 n = .00 E = 1.91 }
151
152 E13f: S-CH -> CH { A = 1.86E+06 n = .00 E = .00 }
153 E14f: S-CH + AR -> CH + AR { A = 3.13E+11 n = .00 E = .00 }
154 E15f: S-CH + N2 -> CH + N2 { A = 3.03E+02 n = 3.40 E = -1.70 }
155 E16f: S-CH + O2 -> CH + O2 { A = 2.48E+06 n = 2.14 E = -7.20 }
156 E17f: S-CH + H2O -> CH + H2O { A = 5.30E+13 n = .00 E = .00 }
157 E18f: S-CH + CO -> CH + CO { A = 2.44E+12 n = 0.50 E = .00 }
158 E19f: S-CH + CO2 -> CH + CO2 { A = 2.40E-01 n = 4.30 E = -7.10 }
159
160
161
162 #=========================================================================#
163 # #
164 # GRI-MECH version 3.0 #
165 # http://www.me.berkeley.edu/gri_mech/ #
166 # #
167 # Gregory P. Smith, David M. Golden, Michael Frenklach, Nigel W. Moriarty #
168 # Boris Eiteneer, Mikhail Goldenberg, C. Thomas Bowman, Ronald K. Hanson, #
169 # Soonho Song, William C. Gardiner, Jr., Vitali V. Lissianski, Zhiwei Qin #
170 # #
171 #=========================================================================#
172
173 # Carbon
174 # ------
175
176 G01f: C + OH -> CO + H { A = 5.00E+13 n = .00 E = .00 }
177 G02f: C + O2 -> CO + O { A = 5.80E+13 n = .00 E = 2.41 }
178
179
180 # Methylidyne
181 # -----------
182
183 # Back to value before GRI opt
184 # Dean, Davidson, Hanson 1991
185 G03f: CH + H -> C + H2 { A = 1.10E+14 n = .00 E = .00 }
186
187 G04f: CH + O -> CO + H { A = 5.70E+13 n = .00 E = .00 }
188 G05f: CH + OH -> HCO + H { A = 3.00E+13 n = .00 E = .00 }
189 G06f: CH + H2 -> T-CH2 + H { A = 1.08E+14 n = .00 E = 13.01 }
190 G07f: CH + H2 + M9 -> CH3 + M9 { A = 4.82E+25 n = -2.80 E = 2.47
191 Ai= 1.97E+12 ni= 0.43 Ei= -1.55
192 fcA = 0.422 fctA = 122
193 fcb = 0.578 fctb = 2535
194 fcc = 1.0 fctc = 9365 }
195 G08f: CH + H2O -> CH2O + H { A = 5.71E+12 n = .00 E = -3.16 }
196 G09f: CH + O2 -> HCO + O { A = 6.71E+13 n = .00 E = .00 }
197 G10f: CH + CO + M9 -> HCCO + M9 { A = 2.69E+28 n = -3.74 E = 8.10
198 Ai= 5.00E+13 ni= .00 Ei= .00
199 fcA = 0.4243 fctA = 237
200 fcb = 0.5757 fctb = 1652
201 fcc = 1.0 fctc = 5069 }
202 G11f: CH + CO2 -> HCO + CO { A = 1.90E+14 n = .00 E = 66.07 }
203
204
205 # Methylene (triplet)
206 # -------------------
207
208 # Ai reduced due to collision limit
209 G12f: T-CH2 + H + M9 -> CH3 + M9 { A = 1.04E+26 n = -2.76 E = 6.69
210 Ai= 4.19E+14 ni= .00 Ei= .00
211 fcA = 0.438 fctA = 91
212 fcb = 0.562 fctb = 5836
213 fcc = 1.0 fctc = 8552 }
214 G13f: T-CH2 + O -> HCO + H { A = 8.00E+13 n = .00 E = .00 }
215 G14f: T-CH2 + OH -> CH2O + H { A = 2.00E+13 n = .00 E = .00 }
216 G15f: T-CH2 + OH -> CH + H2O { A = 1.13E+07 n = 2.00 E = 12.55 }
217 G16f: T-CH2 + H2 -> CH3 + H { A = 5.00E+05 n = 2.00 E = 30.25 }
218
219 # Alvarez, Moore, 1994
220 # Lee, Matsui, Chen, Wang 2012
221 # (revised branching ratios 0.58/0.20/0.22)
222 G17f: T-CH2 + O2 -> HCO + OH { A = 9.57E+12 n = .00 E = 7.27 }
223 G18f: T-CH2 + O2 -> CH2O + O { A = 3.30E+12 n = .00 E = 7.27 }
224 G19f: T-CH2 + O2 -> CO2 + H2 { A = 3.63E+12 n = .00 E = 7.27 }
225
226 G20f: T-CH2 + HO2 -> CH2O + OH { A = 2.00E+13 n = .00 E = .00 }
227 G21f: T-CH2 + C -> C2H + H { A = 5.00E+13 n = .00 E = .00 }
228 G22f: T-CH2 + CO + M9 -> CH2CO + M9 { A = 2.69E+33 n = -5.11 E = 29.69
229 Ai= 8.10E+11 ni= .50 Ei= 18.87
230 fcA = 0.4093 fctA = 275
231 fcb = 0.5907 fctb = 1226
232 fcc = 1.0 fctc = 5185 }
233 G23f: T-CH2 + CH -> C2H2 + H { A = 4.00E+13 n = .00 E = .00 }
234 G24f: T-CH2 + T-CH2 -> C2H2 + H2 { A = 1.60E+15 n = .00 E = 49.97 }
235 G25 : T-CH2 + T-CH2 -> C2H2 + 2 H { A = 2.00E+14 n = .00 E = 45.98 }
236
237
238 # Methylene (singlet)
239 # -------------------
240
241 G26f: S-CH2 + N2 -> T-CH2 + N2 { A = 1.50E+13 n = .00 E = 2.51 }
242 G27f: S-CH2 + AR -> T-CH2 + AR { A = 9.00E+12 n = .00 E = 2.51 }
243 G28f: S-CH2 + CO -> T-CH2 + CO { A = 9.00E+12 n = .00 E = .00 }
244 G29f: S-CH2 + CO2 -> T-CH2 + CO2 { A = 7.00E+12 n = .00 E = .00 }
245 G30f: S-CH2 + H2O -> T-CH2 + H2O { A = 3.00E+13 n = .00 E = .00 }
246
247 G31f: S-CH2 + H -> CH + H2 { A = 3.00E+13 n = .00 E = .00 }
248 G32f: S-CH2 + O -> CO + H2 { A = 1.50E+13 n = .00 E = .00 }
249 G33f: S-CH2 + O -> HCO + H { A = 1.50E+13 n = .00 E = .00 }
250 G34f: S-CH2 + H2 -> CH3 + H { A = 7.00E+13 n = .00 E = .00 }
251 G35 : S-CH2 + O2 -> CO + OH + H { A = 2.80E+13 n = .00 E = .00 }
252 G36f: S-CH2 + O2 -> CO + H2O { A = 1.20E+13 n = .00 E = .00 }
253 G37f: S-CH2 + H2O + M9 -> CH3OH + M9 { A = 1.88E+38 n = -6.36 E = 21.09
254 Ai= 4.82E+17 ni= -1.16 Ei= 4.79
255 fcA = 0.3973 fctA = 208
256 fcb = 0.6027 fctb = 3922
257 fcc = 1.0 fctc = 10180 }
258
259 G38f: S-CH2 + OH -> CH2O + H { A = 3.00E+13 n = .00 E = .00 }
260 G39 : S-CH2 + H2O -> CH2O + H2 { A = 6.82E+10 n = .25 E = -3.91 }
261 G40f: S-CH2 + CO2 -> CH2O + CO { A = 1.40E+13 n = .00 E = .00 }
262
263
264 # Formaldehyde
265 # ------------
266
267 # Fridrichs, Davidson, Hanson 2004
268 # k0 fitted to reproduce k(1atm) - Same Fc as before
269 G41f: CH2O + M9 -> HCO + H + M9 { A = 1.11E+40 n = -6.42 E = 420.33
270 Ai= 8.36E+17 ni= -0.50 Ei= 373.00
271 fcA = 0.2176 fctA = 271
272 fcb = 0.7824 fctb = 2755
273 fcc = 1.0 fctc = 6570 }
274 G42f: CH2O + M9 -> CO + H2 + M9 { A = 1.47E+45 n = -7.83 E = 405.10
275 Ai= 1.23E+14 ni= .00 Ei= 347.00
276 fcA = 0.068 fctA = 197
277 fcb = 0.932 fctb = 1540
278 fcc = 1.0 fctc = 10300 }
279
280 # Wang, Dames, Davidson, Hanson 2014
281 G43f: CH2O + H -> HCO + H2 { A = 5.86E+03 n = 3.13 E = 6.34 }
282
283 # Xu, Zhu, Lin 2006
284 G44f: CH2O + OH -> HCO + H2O { A = 1.94E+06 n = 2.11 E = -7.06 }
285
286 G45f: CH2O + O -> HCO + OH { A = 3.90E+13 n = .00 E = 14.81 }
287 G46f: CH2O + O2 -> HCO + HO2 { A = 1.00E+14 n = .00 E = 167.36 }
288 G47f: CH2O + HO2 -> HCO + H2O2 { A = 5.60E+06 n = 2.00 E = 50.21 }
289
290 # Nguyen, Nguyen, Nguyen, Hoang, Vereecken 2014
291 # (reduced due to collision limit)
292 G48f: CH2O + CH -> CH2CO + H { A = 2.68E+14 n = -0.32 E = -3.21 }
293
294
295 # Methyl radical
296 # --------------
297
298 # Golden 2013
299 # Baulch et al.; Troe Ushakov
300 G49f: CH3 + H + M9 -> CH4 + M9 { A = 2.79E+34 n = -5.10 E = 11.65
301 Ai= 4.36E+13 ni= 0.19 Ei= .00
302 fcA = 0.37 fctA = 61
303 fcb = 0.63 fctb = 3315
304 fcc = 1.0 fctc = 1e10 }
305
306 # Harding, Klippenstein, Georgievskii 2005
307 # Reactions lumped - Products changed
308 G50f: CH3 + O -> CH2O + H { A = 5.54E+13 n = 0.05 E = -0.57 }
309
310 G51f: CH3 + OH + M9 -> CH3OH + M9 { A = 4.00E+36 n = -5.92 E = 13.14
311 Ai= 2.79E+18 ni= -1.43 Ei= 5.57
312 fcA = 0.588 fctA = 195
313 fcb = 0.412 fctb = 5900
314 fcc = 1.0 fctc = 6394 }
315 G52f: CH3 + OH -> T-CH2 + H2O { A = 5.60E+07 n = 1.60 E = 22.68 }
316 G53f: CH3 + OH -> S-CH2 + H2O { A = 6.44E+17 n = -1.34 E = 5.93 }
317 G54: CH3 + OH -> CH2O + H2 { A = 8.00E+09 n = .00 E = -7.34 }
318
319 # Petersen et al. 2007
320 G55f: CH3 + O2 -> CH3O + O { A = 1.38E+13 n = .00 E = 127.70 }
321 G56f: CH3 + O2 -> CH2O + OH { A = 5.87E+11 n = .00 E = 57.91 }
322 G57f: CH3 + O2 + M0 -> CH3O2 + M0 { A = 3.82E+31 n = -4.89 E = 14.36
323 Ai= 1.01E+08 ni= 1.63 Ei= .00
324 fca = 0.955 fcta = 880.1
325 fcb = 0.045 fctb = 2.5E+9
326 fcc = 1 fctc = 1.786E+09 }
327 G58f: CH3O2 + CH3 -> CH3O + CH3O { A = 1.00E+13 n = .00 E = -5.02 }
328 G59 : CH3O2 + CH3O2 -> CH3O + CH3O + O2 { A = 1.40E+16 n = -1.61 E = 7.78 }
329 G60 : CH3O2 + HO2 -> CH3O + OH + O2 { A = 2.47E+11 n = .00 E = -6.57 }
330 G61 : CH3O2 + CH2O -> CH3O + OH + HCO { A = 1.99E+12 n = .00 E = 48.83 }
331
332 # Jasper, Klippensteion, Harding 2009
333 G62f: CH3 + HO2 -> CH3O + OH { A = 1.00E+12 n = 0.29 E = -2.87 }
334 G63f: CH3 + HO2 -> CH4 + O2 { A = 1.19E+05 n = 2.23 E = -12.65 }
335
336 G64f: CH3 + H2O2 -> CH4 + HO2 { A = 2.45E+04 n = 2.47 E = 21.67 }
337 G65f: CH3 + HCO -> CH4 + CO { A = 2.65E+13 n = .00 E = .00 }
338 G66f: CH3 + CH2O -> CH4 + HCO { A = 3.32E+03 n = 2.81 E = 24.52 }
339
340 G67f: CH3 + C -> C2H2 + H { A = 5.00E+13 n = .00 E = .00 }
341 G68f: CH3 + CH -> C2H3 + H { A = 3.00E+13 n = .00 E = .00 }
342 G69f: CH3 + T-CH2 -> C2H4 + H { A = 1.00E+14 n = .00 E = .00 }
343 G70f: CH3 + S-CH2 -> C2H4 + H { A = 1.20E+13 n = .00 E = -2.39 }
344 G71f: CH3 + CH3 -> C2H5 + H { A = 6.84E+12 n = 0.10 E = 44.35 }
345
346
347 # Methoxy radical
348 # ---------------
349
350 # Dames & Golden 2013
351 G72f: CH2OH + M9 -> CH2O + H + M9 { A = 3.50E+21 n = -1.99 E = 100.41
352 Ai= 7.37E+10 ni= 0.81 Ei= 165.61
353 fcA = 0.156 fctA = 900
354 fcb = 0.844 fctb = 1
355 fcc = 1.0 fctc = 3315 }
356 G73f: CH3O + M9 -> CH2O + H + M9 { A = 6.02E+16 n = -0.55 E = 75.41
357 Ai= 1.13E+10 ni= 1.21 Ei= 100.77
358 fcA = 0.659 fctA = 28
359 fcb = 0.341 fctb = 1000
360 fcc = 1.0 fctc = 2339 }
361
362 G75f: CH3O + H + M9 -> CH3OH + M9 { A = 4.66E+41 n = -7.44 E = 58.91
363 Ai= 2.43E+12 ni= .52 Ei= 0.21
364 fcA = 0.30 fctA = 100
365 fcb = 0.70 fctb = 90000
366 fcc = 1.0 fctc = 10000 }
367 G76f: CH3O + H -> CH3 + OH { A = 1.50E+12 n = 0.50 E = -0.46 }
368 G77f: CH3O + H -> S-CH2 + H2O { A = 2.62E+14 n = -0.23 E = 4.48 }
369
370 G78f: CH3O + H -> CH2O + H2 { A = 2.00E+13 n = .00 E = .00 }
371 G79f: CH3O + O -> CH2O + OH { A = 1.00E+13 n = .00 E = .00 }
372 G80f: CH3O + OH -> CH2O + H2O { A = 5.00E+12 n = .00 E = .00 }
373
374 # Baulch et al. 2005
375 G81f: CH3O + O2 -> CH2O + HO2 { A = 6.17E+10 n = .00 E = 7.32 }
376
377 G82f: CH2OH + H + M9 -> CH3OH + M9 { A = 4.36E+31 n = -4.65 E = 21.26
378 Ai= 1.06E+12 ni= 0.50 Ei= 0.36
379 fcA = 0.400 fctA = 100
380 fcb = 0.600 fctb = 9000
381 fcc = 1.0 fctc = 10000 }
382 G83f: CH2OH + H -> CH3 + OH { A = 1.65E+11 n = 0.65 E = -1.19 }
383 G84f: CH2OH + H -> S-CH2 + H2O { A = 3.28E+13 n = -0.09 E = 2.55 }
384
385 G85f: CH2OH + H -> CH2O + H2 { A = 2.00E+13 n = .00 E = .00 }
386 G86f: CH2OH + O -> CH2O + OH { A = 1.00E+13 n = .00 E = .00 }
387 G87f: CH2OH + OH -> CH2O + H2O { A = 5.00E+12 n = .00 E = .00 }
388 G88f: CH2OH + O2 -> CH2O + HO2 { A = 1.80E+13 n = .00 E = 3.77 }
389
390 G89f: CH3O + H -> CH2OH + H { A = 4.15E+07 n = 1.63 E = 8.05 }
391
392
393 # Methane
394 # -------
395
396 G90f: CH4 + H -> CH3 + H2 { A = 6.60E+08 n = 1.62 E = 45.36 }
397 G91f: CH4 + O -> CH3 + OH { A = 1.02E+09 n = 1.50 E = 35.98 }
398 G92f: CH4 + OH -> CH3 + H2O { A = 1.00E+08 n = 1.60 E = 13.05 }
399 G94f: CH4 + T-CH2 -> CH3 + CH3 { A = 2.46E+06 n = 2.00 E = 34.60 }
400 G95f: CH4 + S-CH2 -> CH3 + CH3 { A = 1.60E+13 n = .00 E = -2.39 }
401
402 G93f: CH4 + CH -> C2H4 + H { A = 6.00E+13 n = .00 E = .00 }
403
404
405 # Methanol
406 # --------
407
408 G96f: CH3OH + H -> CH2OH + H2 { A = 1.70E+07 n = 2.10 E = 20.38 }
409 G97f: CH3OH + O -> CH2OH + OH { A = 3.88E+05 n = 2.50 E = 12.97 }
410 G98f: CH3OH + OH -> CH2OH + H2O { A = 1.44E+06 n = 2.00 E = -3.52 }
411 G99f: CH3OH + CH3 -> CH2OH + CH4 { A = 3.00E+07 n = 1.50 E = 41.59 }
412
413 G100f: CH3OH + H -> CH3O + H2 { A = 4.20E+06 n = 2.10 E = 20.38 }
414 G101f: CH3OH + O -> CH3O + OH { A = 1.30E+05 n = 2.50 E = 20.92 }
415 G102f: CH3OH + OH -> CH3O + H2O { A = 6.30E+06 n = 2.00 E = 6.28 }
416 G103f: CH3OH + CH3 -> CH3O + CH4 { A = 1.00E+07 n = 1.50 E = 41.59 }
417
418
419 # Acetyl radical
420 # --------------
421
422 G104f: C2H + H + M9 -> C2H2 + M9 { A = 2.60E+33 n = -4.80 E = 7.95
423 Ai= 1.00E+17 ni= -1.00 Ei= .00
424 fcA = 0.3536 fctA = 132
425 fcb = 0.6464 fctb = 1315
426 fcc = 1.0 fctc = 5566 }
427 G105f: C2H + O -> CH + CO { A = 5.00E+13 n = .00 E = .00 }
428 G106f: C2H + OH -> HCCO + H { A = 2.00E+13 n = .00 E = .00 }
429 G107f: C2H + O2 -> HCO + CO { A = 1.00E+13 n = .00 E = -3.16 }
430
431 # Carl, Vereecken & Peeters 2007
432 G108f: C2H + H2 -> C2H2 + H { A = 2.36E+05 n = 2.57 E = 1.08 }
433
434
435 # Ketenyl radical
436 # ---------------
437
438 G109f: HCCO + H -> S-CH2 + CO { A = 1.00E+14 n = .00 E = .00 }
439 G110f: HCCO + CH -> C2H2 + CO { A = 5.00E+13 n = .00 E = .00 }
440 G111f: HCCO + T-CH2 -> C2H3 + CO { A = 3.00E+13 n = .00 E = .00 }
441 G112f: HCCO + CH3 -> C2H4 + CO { A = 5.00E+13 n = .00 E = .00 }
442
443 # Chikan, Leone 2005
444 G113 : HCCO + O -> HCO + CO { A = 7.83E+13 n = .00 E = .00 }
445 G114 : HCCO + O -> CO2 + CH { A = 4.82E+12 n = .00 E = .00 }
446
447 # Mai, Raghunath, Le, Huynh, Nam, Lin 2014
448 # Assumed decomposition of HCOH into HCO+H
449 G115 : HCCO + OH -> CO + HCO + H { A = 2.62E+15 n = -0.41 E = 4.21 }
450 G116f: HCCO + OH -> T-CH2 + CO2 { A = 8.97E+04 n = 2.09 E = -9.19 }
451
452 # Klippenstein, Miller, Harding 2002
453 G117 : HCCO + O2 -> CO2 + CO + H { A = 4.78E+12 n = -0.14 E = 4.81 }
454 G118 : HCCO + O2 -> 2CO + OH { A = 1.91E+11 n = -0.02 E = 4.28 }
455
456
457 # Acetylene
458 # ---------
459
460 # Miller & Klippenstein 2004
461 # Refitted TROE form
462 G119f: C2H2 + H + M9 -> C2H3 + M9 { A = 9.06E+31 n = -4.66 E = 15.82
463 Ai= 1.71E+10 ni= 1.27 Ei= 11.33
464 fcA = 0.751 fctA = 12.1
465 fcb = 0.249 fctb = 10000
466 fcc = 1.0 fctc = 5493 }
467
468 # Nguyen, Vereecken, Peeters 2006 - Total rate
469 # Rajak & Maiti 2010 - Branching ratios
470 G120f: C2H2 + O -> HCCO + H { A = 2.96E+09 n = 1.28 E = 10.34 }
471 G121f: C2H2 + O -> T-CH2 + CO { A = 7.40E+08 n = 1.28 E = 10.34 }
472
473 # Tsang & Hampson 1986
474 # Modified for Collision Limit
475 G122f: C2H + OH -> C2H2 + O { A = 1.81E+13 n = .00 E = .00 }
476
477 # Senosiain, Klippenstein & Miller 2005
478 # HCCOH lumped into CH2CO
479 G123f: C2H2 + OH -> C2H + H2O { A = 2.63E+06 n = 2.14 E = 71.38 }
480 G124f: C2H2 + OH -> CH2CO + H { A = 2.10E+01 n = 3.22 E = -1.76 }
481 G125f: C2H2 + OH -> CH3 + CO { A = 1.28E+09 n = 0.73 E = 10.79 }
482
483 # Laskin & Wang 1999
484 G126f: C2H2 + M9 -> H2C2 + M9 { A = 2.45E+15 n = -0.64 E = 207.94 }
485 G127f: H2C2 + O2 -> 2 HCO { A = 1.00E+13 n = .00 E = .00 }
486
487
488 # Ketene
489 # ------
490 # Updated by Eiteneer & Frenklach 2003
491
492 G128f: CH2CO + H -> HCCO + H2 { A = 5.00E+13 n = .00 E = 33.47 }
493 G129f: CH2CO + O -> HCCO + OH { A = 1.00E+13 n = .00 E = 33.47 }
494 G130f: CH2CO + OH -> HCCO + H2O { A = 7.50E+12 n = .00 E = 8.37 }
495 G131f: CH2CO + T-CH2 -> HCCO + CH3 { A = 3.60E+13 n = .00 E = 46.02 }
496
497 # Woods & Haynes 1994
498 G132f: CH2CO + CH3 -> HCCO + CH4 { A = 7.50E+12 n = .00 E = 54.39 }
499 G133f: CH2CO + CH3 -> C2H5 + CO { A = 9.00E+10 n = .00 E = .00 }
500
501 # Senosiain, Klippenstein & Miller 2006
502 G134f: CH2CO + H -> CH3 + CO { A = 7.77E+08 n = 1.45 E = 11.63 }
503
504 # Lee & Bozzelli 2002
505 G135f: CH2CO + OH -> CH2OH + CO { A = 5.00E+12 n = .00 E = .00 }
506 G136f: CH2CO + T-CH2 -> C2H4 + CO { A = 1.00E+12 n = .00 E = .00 }
507
508 G137f: CH2CO + O -> T-CH2 + CO2 { A = 1.75E+12 n = .00 E = 5.65 }
509
510
511 # Vinyl radical
512 # -------------
513
514 G138f: C2H3 + H + M9 -> C2H4 + M9 { A = 1.40E+30 n = -3.86 E = 13.89
515 Ai= 6.08E+12 ni= 0.27 Ei= 1.17
516 fcA = 0.218 fctA = 207.5
517 fcb = 0.782 fctb = 2663
518 fcc = 1.0 fctc = 6095 }
519 G139f: C2H3 + H -> C2H2 + H2 { A = 3.00E+13 n = .00 E = .00 }
520
521 # Harding, Klippenstein & Georgievskii 2005
522 G140f: C2H3 + O -> CH3 + CO { A = 1.03E+13 n = 0.21 E = -1.79 }
523
524 G141f: C2H3 + OH -> C2H2 + H2O { A = 5.00E+12 n = .00 E = .00 }
525 G142f: C2H3 + O2 -> C2H2 + HO2 { A = 1.34E+06 n = 1.61 E = -1.61 }
526
527 # Stoliarov et al. 2002
528 G143f: C2H3 + CH3 -> C2H2 + CH4 { A = 9.03E+12 n = .00 E = -3.20 }
529
530 # Oguchi, Sato, Matsui 2009
531 # Matsugi, Miyoshi 2014
532 G144f: C2H3 + O2 -> CH2CHO + O { A = 3.80E+11 n = 0.19 E = 0.20 }
533 G145f: C2H3 + O2 -> CH2O + HCO { A = 4.05E+17 n = -1.86 E = 4.88 }
534 G146 : C2H3 + O2 -> CH2O + CO + H { A = 2.22E+16 n = -1.35 E = 3.28 }
535
536 G147f: C2H3 + H2O2 -> C2H4 + HO2 { A = 1.21E+10 n = .00 E = -2.49 }
537 G148f: C2H3 + HCO -> C2H4 + CO { A = 9.00E+13 n = .00 E = .00 }
538
539
540 # CH2CHO
541 # ------
542
543 # Senosiain, Klippenstein & Miller 2006
544 G149f: CH2CHO -> CH2CO + H { A = 1.32E+34 n = -6.57 E = 202.45 }
545 G150f: CH2CHO -> CH3 + CO { A = 6.51E+34 n = -6.87 E = 197.46 }
546
547 # Same as for C2H5 + O
548 G151f: CH2CHO + O -> CH2O + HCO { A = 3.17E+13 n = 0.03 E = -1.65 }
549
550 G152 : CH2CHO + O2 -> CH2O + CO + OH { A = 1.81E+10 n = .00 E = 0.00 }
551 G153 : CH2CHO + O2 -> 2 HCO + OH { A = 2.35E+10 n = .00 E = 0.00 }
552 G154f: CH2CHO + H -> CH2CO + H2 { A = 1.10E+13 n = .00 E = 0.00 }
553 G155f: CH2CHO + OH -> CH2CO + H2O { A = 1.20E+13 n = .00 E = 0.00 }
554
555 G156f: CH2CHO + H -> CH3 + HCO { A = 2.20E+13 n = .00 E = 0.00 }
556 G157f: CH2CHO + OH -> CH2OH + HCO { A = 3.01E+13 n = .00 E = 0.00 }
557 G158f: CH2CHO + CH3 -> C2H5 + HCO { A = 4.90E+14 n = -0.50 E = .00 }
558
559
560 # Acetaldehyde
561 # ------------
562 # Mendes, Zhou, Curran 2014
563 # (O/O2 rates as before/CH2O)
564 # (OH rate from CH2O x 0.5)
565
566 # Sivaramakrishnan, Michael, Klippenstein 2010
567 G159f: CH3CHO + M9 -> CH3 + HCO + M9 { A = 1.63E+59 n =-11.34 E = 401.32
568 Ai= 2.72E+22 ni= -1.74 Ei= 361.33
569 fcA = 0.0 fctA = 1
570 fcb = 0.0 fctb = 1
571 fcc = 0.138 fctc = -670 }
572 G160 : CH3CHO + H -> CH3 + CO + H2 { A = 1.31E+05 n = 2.58 E = 5.10 }
573 G161f: CH3CHO + H -> CH2CHO + H2 { A = 2.72E+03 n = 3.10 E = 21.78 }
574
575 G162 : CH3CHO + O -> CH3 + CO + OH { A = 1.95E+13 n = .00 E = 14.81 }
576 G163 : CH3CHO + OH -> CH3 + CO + H2O { A = 9.70E+05 n = 2.11 E = -7.06 }
577 G164 : CH3CHO + O2 -> CH3 + CO + HO2 { A = 5.00E+13 n = .00 E = 167.36 }
578 G165 : CH3CHO + HO2 -> CH3 + CO + H2O2 { A = 2.78E-03 n = 4.50 E = 20.20 }
579 G166 : CH3CHO + CH3 -> CH3 + CO + CH4 { A = 1.55E+00 n = 3.70 E = 19.10 }
580
581 G167f: CH3CHO + O -> CH2CHO + OH { A = 2.92E+12 n = .00 E = 7.57 }
582 G168f: CH3CHO + OH -> CH2CHO + H2O { A = 6.06E-01 n = 3.90 E = -4.47 }
583 G169f: CH3CHO + HO2 -> CH2CHO + H2O2 { A = 5.43E-02 n = 4.10 E = 78.02 }
584 G170f: CH3CHO + CH3 -> CH2CHO + CH4 { A = 1.44E+00 n = 3.70 E = 37.06 }
585
586
587 # Ethylene
588 # --------
589
590 # Ren, Davidson, Hanson 2012
591 G171 : C2H4 + M9 -> H2C2 + H2 + M9 { A = 3.71E+16 n = .00 E = 283.76 }
592
593 # Miller & Klippenstein 2004
594 # Refitted TROE form
595 G172f: C2H4 + H + M9 -> C2H5 + M9 { A = 2.89E+39 n = -6.64 E = 24.14
596 Ai= 1.37E+09 ni= 1.46 Ei= 5.67
597 fcA = 0.74 fctA = 361.7
598 fcb = 0.26 fctb = 10000
599 fcc = 1.0 fctc = 9096 }
600
601 # Tautermann, Wellenzohn, Clary 2006 (written as reversed)
602 # 10% larger than Huynh, Panasewicz, Ratkiewicz, Truong 2007
603 # Close to the recommendation of Baulch et al. 2005
604 G173f: C2H4 + H -> C2H3 + H2 { A = 1.16E+07 n = 2.23 E = 55.80 }
605
606 # Nguyen, Vereecken, Hou, Nguyen, Peeters 2005
607 G174f: C2H4 + O -> CH2CHO + H { A = 7.66E+09 n = 0.88 E = 4.77 }
608 G175f: C2H4 + O -> T-CH2 + CH2O { A = 7.15E+04 n = 2.47 E = 3.89 }
609 G176f: C2H4 + O -> CH3 + HCO { A = 3.89E+08 n = 1.36 E = 3.71 }
610
611 # Vasu, Hong, Davidson, Hanson, Golden 2010
612 G177f: C2H4 + OH -> C2H3 + H2O { A = 2.23E+04 n = 2.75 E = 9.27 }
613
614 # Wang 2001
615 G178f: C2H4 + O2 -> C2H3 + HO2 { A = 4.22E+13 n = .00 E = 259.83 }
616 G179 : C2H4 + O2 -> CH3 + CO2 + H { A = 4.90E+12 n = 0.42 E = 317.15 }
617
618 # Miller & Klippenstein 2013
619 G180f: C2H4 + CH3 -> C2H3 + CH4 { A = 2.06E-01 n = 3.94 E = 51.98 }
620
621 G181f: C2H4 + CH3 + M9 -> N-C3H7 + M9 { A = 3.00E+63 n = -14.6 E = 76.02
622 Ai= 2.55E+06 ni= 1.60 Ei= 23.85
623 fcA = 0.8106 fctA = 277
624 fcb = 0.1894 fctb = 8748
625 fcc = 1.0 fctc = 7891 }
626
627
628 # Ethyl radical
629 # -------------
630
631 G182f: C2H5 + H + M9 -> C2H6 + M9 { A = 1.99E+41 n = -7.08 E = 27.97
632 Ai= 5.21E+17 ni= -0.99 Ei= 6.61
633 fcA = 0.1578 fctA = 125
634 fcb = 0.8422 fctb = 2219
635 fcc = 1.0 fctc = 6882 }
636
637 G183f: C2H5 + H -> C2H4 + H2 { A = 2.00E+12 n = .00 E = .00 }
638
639 # Miller, Klippenstein & Robertson 2000
640 G184f: C2H5 + O2 -> C2H4 + HO2 { A = 1.92E+07 n = 1.02 E = -8.51 }
641
642 # Zhu, Xu & Lin 2004
643 G185f: C2H5 + CH3 -> C2H4 + CH4 { A = 1.18E+04 n = 2.45 E = 12.22 }
644
645 # Harding, Klippenstein & Georgievskii 2005
646 G186f: C2H5 + O -> CH3 + CH2O { A = 3.17E+13 n = 0.03 E = -1.65 }
647
648 # Ludwig et al. 2006
649 G187f: C2H5 + HO2 -> C2H5O + OH { A = 3.10E+13 n = .00 E = .00 }
650
651 G188f: C2H5 + HCO -> C2H6 + CO { A = 1.20E+14 n = .00 E = .00 }
652 G189f: C2H5 + HO2 -> C2H6 + O2 { A = 3.00E+11 n = .00 E = .00 }
653 G190f: C2H5 + HO2 -> C2H4 + H2O2 { A = 3.00E+11 n = .00 E = .00 }
654
655
656 # Ethoxy radical
657 # --------------
658
659 # Dames 2014
660 G191f: C2H5O + M9 -> CH3 + CH2O + M9 { A = 4.70E+25 n = -3.00 E = 69.17
661 Ai= 6.31E+10 ni= 0.93 Ei= 71.54
662 fcA = 0.574 fctA = 0.3
663 fcb = 0.426 fctb = 2046
664 fcc = 1.0 fctc = 1e5 }
665
666 # Baulch et al. 2005
667 G192f: C2H5O + O2 -> CH3CHO + HO2 { A = 2.29E+10 n = .00 E = 3.66 }
668
669
670 # Ethane
671 # ------
672
673 # Oehlschlaeger et al. 2005
674 G193f: C2H6 + M9 -> 2 CH3 + M9 { A = 3.72E+65 n =-13.14 E = 425.01
675 Ai= 1.88E+50 ni= -9.72 Ei= 449.12
676 fcA = 0.61 fctA = 100
677 fcb = 0.39 fctb = 1900
678 fcc = 1.0 fctc = 6000 }
679
680 # Chakraborty, Zhao, Lin, & Truhlar 2006
681 # Fit 500-2000K
682 G194f: C2H6 + H -> C2H5 + H2 { A = 1.70E+05 n = 2.70 E = 24.02 }
683
684 # Huynh, Zhang, Truong 2008
685 G195f: C2H6 + O -> C2H5 + OH { A = 3.17E+01 n = 3.80 E = 13.10 }
686
687 # Krasnoperov & Michael 2004
688 G196f: C2H6 + OH -> C2H5 + H2O { A = 1.61E+06 n = 2.22 E = 3.10 }
689
690 # Carstensen & Dean 2005
691 G197f: C2H6 + HO2 -> C2H5 + H2O2 { A = 2.61E+02 n = 3.37 E = 66.58 }
692
693 G198f: C2H6 + S-CH2 -> C2H5 + CH3 { A = 4.00E+13 n = .00 E = -2.30 }
694
695 # Peukert, Labbe, Sivaramakrishnan, Michael 2013
696 G199f: C2H6 + CH3 -> C2H5 + CH4 { A = 3.45E+01 n = 3.44 E = 43.47 }
697
698
699 # Propyl radicals
700 # ---------------
701
702
703 # Curran 2006 - HPL
704 G200f: C3H6 + H + M9 -> N-C3H7 + M9 { A = 6.26E+38 n = -6.66 E = 29.29
705 Ai= 2.50E+11 ni= 0.51 Ei= 10.96
706 fcA = 0.0 fctA = 1000
707 fcb = 1.0 fctb = 1310
708 fcc = 1.0 fctc = 48097 }
709 G201f: C3H6 + H + M9 -> I-C3H7 + M9 { A = 8.70E+42 n = -7.50 E = 19.75
710 Ai= 4.24E+11 ni= 0.51 Ei= 5.15
711 fcA = 0.0 fctA = 1000
712 fcb = 1.0 fctb = 645.4
713 fcc = 1.0 fctc = 6844.3 }
714
715 G202f: N-C3H7 + H -> C2H5 + CH3 { A = 3.70E+24 n = -2.92 E = 52.32 }
716 G203f: I-C3H7 + H -> C2H5 + CH3 { A = 1.40E+28 n = -3.94 E = 66.59 }
717 G204f: N-C3H7 + H -> C3H6 + H2 { A = 1.80E+12 n = .00 E = .00 }
718 G205f: I-C3H7 + H -> C3H6 + H2 { A = 3.20E+12 n = .00 E = .00 }
719 G206f: N-C3H7 + O -> C2H5 + CH2O { A = 9.60E+13 n = .00 E = .00 }
720 G207f: I-C3H7 + O -> CH3CHO + CH3 { A = 9.60E+13 n = .00 E = .00 }
721 G208f: N-C3H7 + OH -> C3H6 + H2O { A = 2.41E+13 n = .00 E = .00 }
722 G209f: I-C3H7 + OH -> C3H6 + H2O { A = 2.41E+13 n = .00 E = .00 }
723
724 # DeSain, Miller, Klippenstein & Taatjes 2003
725 G210f: N-C3H7 + O2 -> C3H6 + HO2 { A = 3.70E+16 n = -1.63 E = 14.30 }
726 G211f: I-C3H7 + O2 -> C3H6 + HO2 { A = 6.70E+20 n = -3.02 E = 10.48 }
727
728 # Knyazev & Slagle 2001 - Total rate
729 # Shafir, Slagle & Knyazev 2003 - Branching ratio
730 G212f: N-C3H7 + CH3 -> C3H6 + CH4 { A = 3.31E+12 n = .00 E = -3.22 }
731
732
733 # Propane
734 # -------
735
736 # From Tsang 1988
737 G213f: N-C3H7 + H + M9 -> C3H8 + M9 { A = 4.42E+61 n =-13.55 E = 47.52
738 Ai= 3.61E+13 ni= .00 Ei= .00
739 fcA = 0.685 fctA = 369
740 fcb = 0.315 fctb = 3285
741 fcc = 1.0 fctc = 6667 }
742 G214f: I-C3H7 + H + M9 -> C3H8 + M9 { A = 1.70E+58 n =-12.08 E = 47.13
743 Ai= 2.40E+13 ni= .00 Ei= .00
744 fcA = 0.502 fctA = 1314
745 fcb = 0.498 fctb = 1314
746 fcc = 1.0 fctc = 50000 }
747
748 # Oehlschlaeger et al. 2005
749 G215f: C3H8 + M9 -> C2H5 + CH3 + M9 { A = 5.64E+74 n =-15.74 E = 413.04
750 Ai= 1.29E+37 ni= -5.84 Ei= 407.47
751 fcA = 0.69 fctA = 50
752 fcb = 0.31 fctb = 3000
753 fcc = 1.0 fctc = 9000 }
754 # Carstensen & Dean 2009
755 G216f: C3H8 + H -> N-C3H7 + H2 { A = 9.36E+07 n = 1.97 E = 34.31 }
756 G217f: C3H8 + H -> I-C3H7 + H2 { A = 7.60E+07 n = 1.86 E = 23.43 }
757
758 G218f: C3H8 + O -> N-C3H7 + OH { A = 1.90E+05 n = 2.68 E = 15.55 }
759 G219f: C3H8 + O -> I-C3H7 + OH { A = 4.76E+04 n = 2.71 E = 8.81 }
760
761 # Sivaramkrishnan, Srinivasan, Su, Michael 2009
762 G220f: C3H8 + OH -> N-C3H7 + H2O { A = 5.15E+03 n = 2.94 E = -1.75 }
763 G221f: C3H8 + OH -> I-C3H7 + H2O { A = 1.81E+05 n = 2.44 E = -2.24 }
764
765 G222f: C3H8 + CH3 -> N-C3H7 + CH4 { A = 9.03E-01 n = 3.65 E = 29.93 }
766 G223f: C3H8 + CH3 -> I-C3H7 + CH4 { A = 1.51E+00 n = 3.46 E = 29.93 }
767 G224f: C3H8 + HO2 -> N-C3H7 + H2O2 { A = 4.76E+04 n = 2.55 E = 69.00 }
768 G225f: C3H8 + HO2 -> I-C3H7 + H2O2 { A = 9.63E+03 n = 2.60 E = 58.20 }
769
770
771
772 #=========================================================================#
773 # #
774 # "Experimental and Modeling Study of Shock-Tube Oxidation of Acetylene" #
775 # B. Eiteneer and M. Frenklach #
776 # Int. J. Chem. Kinet. 35, 391:414 (2003) #
777 # #
778 #=========================================================================#
779
780
781 # Propynylidene
782 # -------------
783
784 # Nguyen, Mebel, Lin, Kaiser 2001
785 # Loison, Bergeat 2008 (reduced to collision rate)
786 R004f: C2H2 + CH -> C3H2 + H { A = 1.89E+14 n = .00 E = .00 }
787
788 # Boullart, Devriendt, Borns, Peeters 1996
789 R005f: C3H2 + O -> C2H + HCO { A = 1.36E+14 n = .00 E = .00 }
790
791 R006f: C3H2 + OH -> C2H2 + HCO { A = 1.00E+13 n = .00 E = .00 }
792 R007f: C3H2 + O2 -> HCCO + CO + H { A = 1.25E+11 n = .00 E = 4.18 }
793 R008f: C3H2 + CH -> C4H2 + H { A = 5.00E+13 n = .00 E = .00 }
794 R009f: C3H2 + T-CH2 -> N-C4H3 + H { A = 5.00E+13 n = .00 E = .00 }
795 R010f: C3H2 + CH3 -> C4H4 + H { A = 5.00E+12 n = .00 E = .00 }
796 R011f: C3H2 + HCCO -> N-C4H3 + CO { A = 1.00E+13 n = .00 E = .00 }
797
798
799 # Propynal
800 # --------
801
802 # Estimated
803 R012f: C2H + HCO -> C3H2O { A = 5.00E+13 n = .00 E = .00 }
804 # From P-C3H4 + H
805 R013f: C3H2O + H -> C2H2 + HCO { A = 3.46E+12 n = 0.44 E = 22.86 }
806
807 # Taken from CH3CHO
808 R014 : C3H2O + H -> C2H + CO + H2 { A = 1.31E+05 n = 2.58 E = 5.10 }
809 R015 : C3H2O + O -> C2H + CO + OH { A = 1.95E+13 n = .00 E = 14.81 }
810 R016 : C3H2O + OH -> C2H + CO + H2O { A = 9.10E+05 n = 2.11 E = -7.06 }
811 R017 : C3H2O + O2 -> C2H + CO + HO2 { A = 5.00E+13 n = .00 E = 167.36 }
812 R018 : C3H2O + HO2 -> C2H + CO + H2O2 { A = 2.78E-03 n = 4.50 E = 20.20 }
813 R019 : C3H2O + CH3 -> C2H + CO + CH4 { A = 1.55E+00 n = 3.70 E = 19.10 }
814
815
816 # Propargyl radical
817 # -----------------
818
819 R020f: C2H2 + HCCO -> C3H3 + CO { A = 1.00E+11 n = .00 E = 12.55 }
820
821 # Tsang & Hampson 1986
822 R021f: C2H + CH3 -> C3H3 + H { A = 2.41E+13 n = .00 E = .00 }
823
824 # Polino, Klippenstein, Harding, Georgievskii 2013
825 R022f: C2H2 + S-CH2 -> C3H3 + H { A = 3.97E+15 n = -0.57 E = -0.02 }
826
827 # 2x rate for C2H3+H
828 R023f: C3H2 + H + M9 -> C3H3 + M9 { A = 2.80E+30 n = -3.86 E = 13.89
829 Ai= 1.02E+13 ni= .27 Ei= 1.17
830 fcA = 0.218 fctA = 207.5
831 fcb = 0.782 fctb = 2663
832 fcc = 1.0 fctc = 6095 }
833
834 # Miller & Klippenstein 2003 (1bar)
835 R024f: C3H3 + H -> C3H2 + H2 { A = 1.10E+10 n = 1.13 E = 58.28 }
836
837 # Adapted from C2H2 + OH
838 R025f: C3H3 + OH -> C2H3CHO { A = 2.10E+01 n = 3.22 E = -1.76 }
839 R026f: C3H3 + OH -> C2H4 + CO { A = 1.28E+09 n = 0.73 E = 10.79 }
840
841 # 1/2 rate for C2H4+OH
842 R027f: C3H3 + OH -> C3H2 + H2O { A = 1.13E+05 n = 2.28 E = 10.32 }
843
844 # Lee, Nam & Choi 2006
845 # Kwon, Nam, Youn, Joo, Lee, & Choi 2006
846 # Slagle, Gmurczyk, Batt & Gutman 1991
847 R029f: C3H3 + O -> C3H2O + H { A = 1.38E+14 n = .00 E = .00 }
848
849 # Hahn, Klippenstein, Miller 2001
850 R030f: C3H3 + O2 -> CH2CO + HCO { A = 1.70E+05 n = 1.70 E = 6.28 }
851
852 R031 : C3H3 + HO2 -> C2H3 + CO + OH { A = 8.00E+11 n = .00 E = .00 }
853
854 # Wang 2001
855 R032f: C3H3 + HO2 -> A-C3H4 + O2 { A = 3.00E+11 n = .00 E = .00 }
856 R033f: C3H3 + HO2 -> P-C3H4 + O2 { A = 3.00E+11 n = .00 E = .00 }
857 R034f: P-C3H4 + O2 -> CH3 + HCO + CO { A = 4.00E+14 n = .00 E = 175.43 }
858
859 R035f: C3H3 + HCO -> A-C3H4 + CO { A = 2.50E+13 n = .00 E = .00 }
860 R036f: C3H3 + HCO -> P-C3H4 + CO { A = 2.50E+13 n = .00 E = .00 }
861 R037f: C3H3 + CH -> I-C4H3 + H { A = 5.00E+13 n = .00 E = .00 }
862
863 # Miller, Melius 1992
864 R038f: C3H3 + T-CH2 -> C4H4 + H { A = 5.00E+13 n = .00 E = .00 }
865
866
867 # Propyne & Allene
868 # ----------------
869
870 # Thiesemann, Clifford, Taatjes, Klippenstein 2001
871 # Zhang, Maksyutenko, Kaiser 2012
872 R200f: C2H4 + CH -> A-C3H4 + H { A = 9.98E+14 n = -0.31 E = .00 }
873
874 # Miller & Klippenstein 2003 (1bar)
875 R039f: A-C3H4 -> P-C3H4 { A = 7.76E+39 n = -7.80 E = 328.22 }
876
877 # Giri, Fernandes, Bentz, Hippler, Olzmann 2011
878 R040f: P-C3H4 + M0 -> C3H3 + H + M0 { A = 2.15E+43 n = -6.81 E = 420.61 }
879 R041f: A-C3H4 + M0 -> C3H3 + H + M0 { A = 2.15E+43 n = -6.81 E = 420.61 }
880
881 # Miller, Senosiain, Klippenstein, Georgievskii 2008
882 # Refitted 800K-2500K - 1bar
883 R042f: A-C3H4 + H -> C2H2 + CH3 { A = 8.95E+13 n = -0.02 E = 47.07 }
884
885 # Sheen, Rosado-Reyes, Tsang 2013
886 R043f: C2H2 + CH3 -> P-C3H4 + H { A = 1.48E+11 n = 0.60 E = 59.86 }
887 R044f: P-C3H4 + H -> A-C3H4 + H { A = 1.58E+18 n = -1.00 E = 50.72 }
888
889 # Miller, Senosiain, Klippenstein, Georgievskii 2008
890 # P=1bar
891 R045f: A-C3H4 + H -> A-C3H5 { A = 2.01E+49 n =-10.77 E = 82.10 }
892 R046f: A-C3H4 + H -> T-C3H5 { A = 6.70E+42 n =-12.46 E = 68.45 }
893 R047f: P-C3H4 + H -> T-C3H5 { A = 8.83E+52 n =-12.36 E = 68.81 }
894 R048f: P-C3H4 + H -> S-C3H5 { A = 1.53E+49 n =-11.97 E = 59.18 }
895
896 # 1/2 the rate for C2H6
897 R049f: P-C3H4 + H -> C3H3 + H2 { A = 8.50E+04 n = 2.70 E = 24.02 }
898 R050f: P-C3H4 + O -> C3H3 + OH { A = 1.59E+01 n = 3.80 E = 13.10 }
899 R051f: P-C3H4 + OH -> C3H3 + H2O { A = 8.05E+05 n = 2.22 E = 3.10 }
900 R052f: P-C3H4 + CH3 -> C3H3 + CH4 { A = 1.73E+01 n = 3.44 E = 43.47 }
901 R053f: P-C3H4 + HO2 -> C3H3 + H2O2 { A = 1.30E+02 n = 3.37 E = 66.58 }
902
903 # Same as for C2H4
904 R054f: A-C3H4 + H -> C3H3 + H2 { A = 1.33E+06 n = 2.53 E = 51.21 }
905 R055f: A-C3H4 + OH -> C3H3 + H2O { A = 1.31E-01 n = 4.20 E = -3.60 }
906 R056f: A-C3H4 + CH3 -> C3H3 + CH4 { A = 2.06E-01 n = 3.94 E = 51.98 }
907 R057f: A-C3H4 + HO2 -> C3H3 + H2O2 { A = 9.76E+10 n = 0.12 E = 97.78 }
908
909 # Nguyen, Peeters & Vereecken 2006 - rate
910 # Leonori, Balucani et al. 2012 - products
911 R058f: A-C3H4 + O -> C2H4 + CO { A = 9.63E+06 n = 2.05 E = 0.75 }
912
913 # Adapted from C2H2+O (half-half)
914 # Zhao, Wu, Zhao et al. 2009 - Products (singlet)
915 # Balucani, Leonori et al. 2014 - Products (triplet)
916 R059f: P-C3H4 + O -> C2H4 + CO { A = 1.85E+09 n = 1.28 E = 10.34 }
917 R959f: P-C3H4 + O -> HCCO + CH3 { A = 1.85E+09 n = 1.28 E = 10.34 }
918
919 # From C2H2 + OH
920 R060f: P-C3H4 + OH -> CH2CO + CH3 { A = 2.10E+01 n = 3.22 E = -1.76 }
921 R061f: P-C3H4 + OH -> C2H5 + CO { A = 1.28E+09 n = 0.73 E = 10.79 }
922
923 R062f: A-C3H4 + C2H -> C2H2 + C3H3 { A = 1.00E+13 n = .00 E = .00 }
924 R063f: P-C3H4 + C2H -> C2H2 + C3H3 { A = 1.00E+13 n = .00 E = .00 }
925
926 # Liu, Maluc, Jonah 1988
927 R064f: A-C3H4 + OH -> CH2CO + CH3 { A = 4.03E+12 n = .00 E = -0.83 }
928
929
930 # Propenal
931 # --------
932
933 R065f: C2H3 + HCO -> C2H3CHO { A = 1.80E+13 n = .00 E = .00 }
934
935 # Baulch et al. 2005 - adapted from CH3CHO
936 R066 : C2H3CHO + H -> C2H3 + CO + H2 { A = 1.31E+05 n = 2.58 E = 5.10 }
937 R067 : C2H3CHO + O -> C2H3 + CO + OH { A = 1.95E+13 n = .00 E = 14.81 }
938 R068 : C2H3CHO + OH -> C2H3 + CO + H2O { A = 9.70E+05 n = 2.11 E = -7.06 }
939 R069 : C2H3CHO + HO2 -> C2H3 + CO + H2O2 { A = 2.78E-03 n = 4.50 E = 20.20 }
940 R070 : C2H3CHO + CH3 -> C2H3 + CO + CH4 { A = 1.55E+00 n = 3.70 E = 10.10 }
941
942
943 # Allyl radicals
944 # --------------
945
946 # Miller, Senosiain, Klippenstein, Georgievskii 2008
947 # Refitted 800K-2500K - P=1bar
948 R071f: C2H2 + CH3 -> S-C3H5 { A = 7.45E+43 n =-10.13 E = 77.50 }
949
950 # Davis, Law, Wang 1999 (1bar)
951 R072f: A-C3H5 -> T-C3H5 { A = 7.06E+56 n =-14.08 E = 317.43 }
952 R073f: A-C3H5 -> S-C3H5 { A = 5.00E+51 n =-13.02 E = 306.69 }
953 R074f: T-C3H5 -> S-C3H5 { A = 1.50E+48 n =-12.71 E = 225.52 }
954
955 # Klippenstein, Harding, Georgievskii, Miller 2008
956 # Fitted 400K-2500K
957 R075f: A-C3H5 + H -> A-C3H4 + H2 { A = 9.56E+03 n = 2.80 E = 13.77 }
958
959 # Tsang 1991
960 R076f: A-C3H5 + OH -> A-C3H4 + H2O { A = 6.03E+12 n = .00 E = .00 }
961 R077f: A-C3H5 + CH3 -> A-C3H4 + CH4 { A = 3.01E+12 n = -0.32 E = -0.55 }
962 R078f: A-C3H5 + C2H3 -> A-C3H4 + C2H4 { A = 2.41E+12 n = .00 E = .00 }
963 R079f: A-C3H5 + C2H5 -> A-C3H4 + C2H6 { A = 9.64E+11 n = .00 E = -0.55 }
964
965 # Lee & Bozzelli 2005
966 R081f: A-C3H5 + O2 -> A-C3H4 + HO2 { A = 2.06E+04 n = 2.19 E = 73.60 }
967 R082f: A-C3H5 + O2 -> C2H3CHO + OH { A = 3.36E+05 n = 1.81 E = 80.29 }
968 R083 : A-C3H5 + O2 -> C2H2 + CH2O + OH { A = 9.71E+20 n = -2.70 E = 104.52 }
969 R084f: A-C3H5 + O2 -> CH2CHO + CH2O { A = 3.08E+09 n = 0.37 E = 70.75 }
970
971 # Estimated from C2H5+O
972 # Park, lee, Choi 2003 - Products
973 R085f: A-C3H5 + O -> C2H3CHO + H { A = 3.17E+13 n = 0.03 E = -1.65 }
974
975 R086 : A-C3H5 + OH -> C2H3CHO + H2 { A = 4.20E+32 n = -5.16 E = 126.05 }
976 R087f: A-C3H5 + HCO -> C3H6 + CO { A = 6.00E+13 n = .00 E = .00 }
977 R088f: A-C3H5 + HO2 -> C3H6 + O2 { A = 2.66E+12 n = .00 E = .00 }
978 # From A1CH2+HO2
979 R089f: A-C3H5 + HO2 -> C3H5O + OH { A = 1.19E+09 n = 1.03 E = -9.41 }
980
981 R090f: T-C3H5 + H -> P-C3H4 + H2 { A = 3.34E+12 n = .00 E = .00 }
982 R091f: T-C3H5 + O -> CH3 + CH2CO { A = 6.00E+13 n = .00 E = .00 }
983 R092 : T-C3H5 + OH -> CH3 + CH2CO + H { A = 5.00E+12 n = .00 E = .00 }
984 R093 : T-C3H5 + HO2 -> CH3 + CH2CO + OH { A = 2.00E+13 n = .00 E = .00 }
985 R094f: T-C3H5 + HCO -> C3H6 + CO { A = 9.00E+13 n = .00 E = .00 }
986 R095f: T-C3H5 + CH3 -> P-C3H4 + CH4 { A = 1.00E+11 n = .00 E = .00 }
987
988 R096f: S-C3H5 + H -> P-C3H4 + H2 { A = 3.34E+12 n = .00 E = .00 }
989 R097f: S-C3H5 + O -> C2H4 + HCO { A = 6.00E+13 n = .00 E = .00 }
990 R098 : S-C3H5 + OH -> C2H4 + HCO + H { A = 5.00E+12 n = .00 E = .00 }
991 R099 : S-C3H5 + HO2 -> C2H4 + HCO + OH { A = 2.00E+13 n = .00 E = .00 }
992 R100f: S-C3H5 + HCO -> C3H6 + CO { A = 9.00E+13 n = .00 E = .00 }
993 R101f: S-C3H5 + CH3 -> P-C3H4 + CH4 { A = 1.00E+11 n = .00 E = .00 }
994
995 # Adapted from C2H5/C2H3+O2
996 R102f: T-C3H5 + O2 -> A-C3H4 + HO2 { A = 1.92E+07 n = 1.02 E = -8.51 }
997 R103f: T-C3H5 + O2 -> P-C3H4 + HO2 { A = 1.34E+06 n = 1.61 E = -1.61 }
998 R104f: S-C3H5 + O2 -> P-C3H4 + HO2 { A = 6.70E+05 n = 1.61 E = -1.61 }
999 R105 : T-C3H5 + O2 -> CH3 + CO + CH2O { A = 4.58E+16 n = -1.39 E = 4.25 }
1000 R106f: S-C3H5 + O2 -> CH3CHO + HCO { A = 4.58E+16 n = -1.39 E = 4.25 }
1001
1002
1003 # Propanone
1004 # ---------
1005
1006 # NC7 path from LLNL
1007 R107f: C3H5O -> C2H3CHO + H { A = 1.00E+14 n = .00 E = 121.75 }
1008 R108f: C3H5O -> C2H3 + CH2O { A = 2.03E+12 n = 0.09 E = 98.58 }
1009 R109f: C3H5O + O2 -> C2H3CHO + HO2 { A = 1.00E+12 n = .00 E = 25.10 }
1010
1011
1012 # Propene
1013 # -------
1014 # A -> 60%-85% C2H6; S -> 20%-50% C2H4; T -> 35% C2H4
1015
1016 # Stoliarov et al. 2002
1017 # Rates fitted at 1.33 bar - 500K to 2400K
1018 R110f: C3H6 -> C2H3 + CH3 { A = 4.04E+42 n = -7.67 E = 467.90 }
1019 R111f: C2H3 + CH3 -> A-C3H5 + H { A = 1.93E+18 n = -1.25 E = 32.09 }
1020
1021 # Harding, Klippenstein, & Georgievskii 2007
1022 # -> High pressure limit
1023 # Stoliarov et al. 2002
1024 # -> Fall-off at 1.33bar - 900K to 3000K
1025 R112f: A-C3H5 + H -> C3H6 { A = 5.93E+54 n =-11.76 E = 98.53 }
1026
1027 # Miller & Klippenstein 2013
1028 # Refitted at P=1bar
1029 R113f: C3H6 + H -> C2H4 + CH3 { A = 2.67E+12 n = 0.47 E = 22.72 }
1030 R114f: C3H6 + H -> A-C3H5 + H2 { A = 1.42E+04 n = 2.82 E = 14.23 }
1031 R115f: C3H6 + H -> S-C3H5 + H2 { A = 8.34E+02 n = 3.25 E = 50.86 }
1032 R116f: C3H6 + H -> T-C3H5 + H2 { A = 1.49E+02 n = 3.38 E = 37.28 }
1033
1034 # Zador, Jasper, Miller 2009
1035 # Vasu, Hong, Davidson, Hanson 2010
1036 R117f: C3H6 + OH -> A-C3H5 + H2O { A = 9.00E+04 n = 2.59 E = 1.74 }
1037 R118f: C3H6 + OH -> S-C3H5 + H2O { A = 3.67E+03 n = 2.89 E = 8.05 }
1038 R119f: C3H6 + OH -> T-C3H5 + H2O { A = 4.67E+04 n = 2.47 E = 7.31 }
1039
1040 # Cavallotti, Leonori, Balucani et al. 2014
1041 # CH3CH replaced by C2H4 - 1bar
1042 R120f: C3H6 + O -> CH2CHO + CH3 { A = 8.12E+08 n = 1.25 E = 2.26 }
1043 R121f: C3H6 + O -> C2H4 + CH2O { A = 3.63E+10 n = 0.82 E = 7.65 }
1044 R123f: C3H6 + O -> A-C3H5 + OH { A = 1.43E+02 n = 3.37 E = 0.73 }
1045
1046 # Rate from C3H8 + X (x0.5)
1047 R124f: C3H6 + HO2 -> A-C3H5 + H2O2 { A = 2.38E+04 n = 2.55 E = 69.00 }
1048 R125f: C3H6 + CH3 -> A-C3H5 + CH4 { A = 4.57E-01 n = 3.65 E = 29.93 }
1049
1050 # From C2H4
1051 R126f: C3H6 + CH3 -> S-C3H5 + CH4 { A = 1.03E-01 n = 3.94 E = 51.98 }
1052 R127f: C3H6 + CH3 -> T-C3H5 + CH4 { A = 5.15E-02 n = 3.94 E = 51.98 }
1053
1054
1055 # Hexadiyene
1056 # ----------
1057
1058 # Lynch, Annesley, Aul, Yang, Tranter 2013
1059 R128f: A-C3H5 + A-C3H5 -> A-C3H4 + C3H6 { A = 7.50E+11 n = .00 E = .00 }
1060 # Matsugi, Suma, Miyoshi 2011
1061 R129 : A-C3H5 + A-C3H5 -> C6H10 { A = 3.18E+13 n = -0.24 E = -2.46 }
1062
1063 # From C3H8 (x2)
1064 R130 : C6H10 + H -> C6H9 + H2 { A = 1.52E+08 n = 1.86 E = 23.43 }
1065 R131 : C6H10 + O -> C6H9 + OH { A = 9.52E+04 n = 2.71 E = 8.81 }
1066 R132 : C6H10 + OH -> C6H9 + H2O { A = 3.62E+05 n = 2.44 E = -2.24 }
1067 R133 : C6H10 + CH3 -> C6H9 + CH4 { A = 3.02E+00 n = 3.46 E = 29.93 }
1068 R134 : C6H10 + HO2 -> C6H9 + H2O2 { A = 1.93E+04 n = 2.60 E = 58.20 }
1069
1070 # From C3H6 (x2)
1071 R135 : C6H10 + H -> C4H7 + C2H4 { A = 5.34E+12 n = 0.47 E = 22.72 }
1072
1073
1074 # Hexadiyenyl radical
1075 # -------------------
1076
1077 # From C2H5
1078 R136 : C6H9 + O -> C2H3CHO + A-C3H5 { A = 3.17E+13 n = 0.03 E = -1.65 }
1079 R137 : C6H9 + HO2 -> C2H3CHO + A-C3H5 + OH { A = 3.10E+13 n = .00 E = .00 }
1080
1081 # From LLNL
1082 R138 : C6H9 -> C4H6 + C2H3 { A = 2.50E+13 n = .00 E = 188.28 }
1083
1084
1085
1086 #==========================================================================#
1087 # #
1088 # "Shock-Tube and Modeling Study of Diacetylene Pyrolysis and Oxidation" #
1089 # Y. Hidaka, Y. Henmi, T. Ohonishi & T. Okuno #
1090 # Combustion and Flame 130:62-82 (2002) #
1091 # #
1092 #==========================================================================#
1093
1094 # Diacetylene
1095 # -----------
1096
1097 # From C2H
1098 H01 : C4H + O2 -> C2H + 2CO { A = 1.00E+13 n = .00 E = -3.16 }
1099
1100 H02f: C4H2 -> C4H + H { A = 2.20E+14 n = .00 E = 487.85 }
1101 H03f: C4H2 + H -> C4H + H2 { A = 2.00E+14 n = .00 E = 108.78 }
1102
1103 # Ceursters, Nguyen, Peeters, Nguyen 2000
1104 H04f: C2H2 + C2H -> C4H2 + H { A = 7.80E+13 n = .00 E = .00 }
1105
1106 # Klippenstein & Miller 2005
1107 # Refitted Rate & TROE form
1108 H05f: C4H2 + H + M9 -> I-C4H3 + M9 { Ai= 4.31E+10 ni= 1.16 Ei= 7.33
1109 A = 2.30E+45 n = -8.10 E = 10.49
1110 fcA = 0.901 fctA = 12.5
1111 fcB = 0.099 fctB = 10000
1112 fcc = 1.0 fctc = 6674 }
1113 H06f: C4H2 + H -> N-C4H3 { A = 1.37E+39 n = -7.87 E = 64.61 }
1114
1115 H07f: C4H2 + O -> C3H2 + CO { A = 2.80E+13 n = .00 E = 7.24 }
1116 H08f: C4H2 + O -> C4H2O { A = 4.00E+13 n = .00 E = .00 }
1117 H09f: C4H2 + O2 -> HCCO + HCCO { A = 9.56E+12 n = .00 E = 130.12 }
1118
1119 # Senosiain, Klippenstein & Miller 2007
1120 H10f: C4H2 + OH -> C4H + H2O { A = 9.15E+09 n = 1.03 E = 90.99 }
1121 H11f: C4H2 + OH -> C4H2O + H { A = 3.41E+10 n = 0.31 E = 5.00 }
1122 H12f: C4H2 + OH -> C3H3 + CO { A = 2.11E+23 n = -3.47 E = 31.76 }
1123
1124
1125 # Ethynylketene
1126 # -------------
1127
1128 H13f: C4H2O + H -> C2H2 + HCCO { A = 5.00E+13 n = .00 E = 12.55 }
1129 H14f: C4H2O + O -> C3H2 + CO2 { A = 1.00E+13 n = .00 E = .00 }
1130 H15f: C4H2O + OH -> CH2CO + HCCO { A = 1.00E+07 n = 2.00 E = 8.37 }
1131
1132
1133 # C4H3 radicals
1134 # -------------
1135
1136 # Wang 1992 ??
1137 H16f: N-C4H3 -> I-C4H3 { A = 4.10E+43 n = -9.50 E = 221.75 }
1138 H17f: N-C4H3 + H -> I-C4H3 + H { A = 2.50E+20 n = -1.67 E = 45.19 }
1139 H18f: N-C4H3 + H -> C4H4 { A = 2.00E+47 n =-10.26 E = 54.69 }
1140 H19f: I-C4H3 + H -> C4H4 { A = 3.40E+43 n = -9.01 E = 50.71 }
1141 H20f: N-C4H3 + H -> C2H2 + H2C2 { A = 6.30E+25 n = -3.34 E = 41.90 }
1142 H21f: I-C4H3 + H -> C2H2 + H2C2 { A = 2.80E+23 n = -2.55 E = 45.10 }
1143
1144 # From C2H3
1145 H22f: N-C4H3 + H -> C4H2 + H2 { A = 1.50E+13 n = .00 E = .00 }
1146 H23f: I-C4H3 + H -> C4H2 + H2 { A = 3.00E+13 n = .00 E = .00 }
1147 H24f: N-C4H3 + OH -> C4H2 + H2O { A = 2.50E+12 n = .00 E = .00 }
1148 H25f: I-C4H3 + OH -> C4H2 + H2O { A = 5.00E+12 n = .00 E = .00 }
1149 H26f: N-C4H3 + O2 -> C4H2 + HO2 { A = 6.70E+05 n = 1.61 E = -1.61 }
1150 H27f: I-C4H3 + O2 -> C4H2 + HO2 { A = 1.34E+06 n = 1.61 E = -1.61 }
1151
1152 H28f: N-C4H3 + O -> C2H2 + HCCO { A = 1.03E+13 n = 0.21 E = -1.79 }
1153 H29f: I-C4H3 + O -> CH2CO + C2H { A = 2.00E+13 n = .00 E = .00 }
1154 H30f: I-C4H3 + O2 -> HCCO + CH2CO { A = 1.63E+11 n = .00 E = -7.53 }
1155
1156
1157 # Vinylacetylene
1158 # --------------
1159
1160 H31f: C4H4 -> C4H2 + H2 { A = 1.30E+15 n = .00 E = 396.14 }
1161 H32f: C4H4 -> C2H2 + C2H2 { A = 3.40E+13 n = .00 E = 322.59 }
1162
1163 # Decomposition of C4H4 revisited
1164 # Problem for diffusion flamelets with C2H2+H2C2
1165 #H30f: C2H3 + C2H -> C4H4 { A = 1.00E+14 n = .00 E = .00 }
1166 #H31f: C2H4 + C2H -> C4H4 + H { A = 1.20E+13 n = .00 E = .00 }
1167
1168 # Miller, Klippenstein & Robertson 2000
1169 H33f: C2H3 + C2H2 -> C4H4 + H { A = 1.32E+12 n = 0.16 E = 34.78 }
1170
1171 # Adapted from C2H4 - 3kcal
1172 H34f: C4H4 + H -> N-C4H3 + H2 { A = 1.16E+07 n = 2.23 E = 55.80 }
1173 H35f: C4H4 + H -> I-C4H3 + H2 { A = 5.80E+06 n = 2.23 E = 43.25 }
1174 H36f: C4H4 + OH -> N-C4H3 + H2O { A = 2.23E+04 n = 2.75 E = 9.27 }
1175 H37f: C4H4 + OH -> I-C4H3 + H2O { A = 1.12E+04 n = 2.75 E = -3.28 }
1176 H38f: C4H4 + CH3 -> N-C4H3 + CH4 { A = 1.03E-01 n = 3.94 E = 51.98 }
1177 H39f: C4H4 + CH3 -> I-C4H3 + CH4 { A = 5.15E-02 n = 3.94 E = 39.43 }
1178
1179 # From C2H4
1180 H40f: C4H4 + O -> C3H3 + HCO { A = 6.00E+08 n = 1.45 E = -3.60 }
1181
1182 # From C2H2
1183 #41f: C4H4 + OH -> CH2CO + C2H3 { A = 2.10E+01 n = 3.22 E = -1.76 }
1184 H42f: C4H4 + OH -> A-C3H5 + CO { A = 1.28E+09 n = 0.73 E = 10.79 }
1185
1186
1187 # Hexatriyne & Octotetrayne
1188 # -------------------------
1189
1190 # Reactions of C6H2 & C8H2
1191 # Ceursters, Nguyen, Peeters, Nguyen 2000
1192 H43f: C4H2 + C2H -> C6H2 + H { A = 7.80E+13 n = .00 E = .00 }
1193 H44f: C2H2 + C4H -> C6H2 + H { A = 7.80E+13 n = .00 E = .00 }
1194 H45f: C6H2 + C2H -> C8H2 + H { A = 7.80E+13 n = .00 E = .00 }
1195 H46f: C4H2 + C4H -> C8H2 + H { A = 7.80E+13 n = .00 E = .00 }
1196
1197 # Estimated
1198 H47f: C4H + C4H -> C8H2 { A = 1.00E+14 n = .00 E = .00 }
1199
1200 # From C4H2 + OH
1201 H48 : C6H2 + OH -> C4H2 + HCCO { A = 3.41E+10 n = 0.31 E = 5.00 }
1202 H49 : C8H2 + OH -> C6H2 + HCCO { A = 3.41E+10 n = 0.31 E = 5.00 }
1203
1204
1205
1206 #==========================================================================#
1207 # #
1208 # "Detailed kinetic modelling of butadiene Oxidation at high temperatures" #
1209 # A. Laskin, H. Wang, C. Law. #
1210 # Int. J. Chem. Kinet. 2000. 32-589 #
1211 # #
1212 #==========================================================================#
1213
1214
1215 # 1,3-Butadiene
1216 # -------------
1217
1218 # Peukert, Naumann, Braun-unkhoff 2009
1219 B01f: C4H6 -> C2H4 + C2H2 { A = 7.00E+12 n = .00 E = 280.75 }
1220
1221 B02f: C2H3 + C2H3 -> C4H6 { A = 1.50E+42 n = -8.84 E = 52.23 }
1222
1223 # Ismail, Georgievskii, Taatjes, et al. 2007
1224 # Rate fitted at 1.33bar
1225 B03f: C2H4 + C2H3 -> C4H6 + H { A = 2.15E+12 n = 0.46 E = 62.65 }
1226
1227 B04f: C3H6 + C2H3 -> C4H6 + CH3 { A = 7.23E+11 n = .00 E = 20.92 }
1228
1229 #B05f: C4H6 + H -> P-C3H4 + CH3 { A = 2.00E+12 n = .00 E = 29.29 }
1230 #B06f: C4H6 + H -> A-C3H4 + CH3 { A = 2.00E+12 n = .00 E = 29.29 }
1231
1232 B07f: C4H6 -> I-C4H5 + H { A = 5.70E+36 n = -6.27 E = 470.09 }
1233 B08f: C4H6 -> N-C4H5 + H { A = 5.30E+44 n = -8.62 E = 517.18 }
1234 B09f: C4H6 -> C4H4 + H2 { A = 2.50E+15 n = .00 E = 396.22 }
1235
1236 # Adapted from C2H4
1237 # Rate for OH from Vasu, Hanson, et al. 2010 - refitted
1238 # Rate for O refitted - 8e11 backward
1239 B10f: C4H6 + H -> N-C4H5 + H2 { A = 1.16E+07 n = 2.23 E = 55.80 }
1240 B11f: C4H6 + O -> N-C4H5 + OH { A = 7.12E+14 n = -0.23 E = 41.03 }
1241 B12f: C4H6 + OH -> N-C4H5 + H2O { A = 1.56E+05 n = 2.46 E = 7.78 }
1242 B13f: C4H6 + O2 -> N-C4H5 + HO2 { A = 4.22E+13 n = .00 E = 259.83 }
1243 B14f: C4H6 + CH3 -> N-C4H5 + CH4 { A = 2.06E-01 n = 3.94 E = 51.98 }
1244 B15f: C4H6 + HO2 -> N-C4H5 + H2O2 { A = 1.66E+10 n = 0.36 E = 95.13 }
1245
1246 # Adapted from C2H4 - 3kcal
1247 B16f: C4H6 + H -> I-C4H5 + H2 { A = 5.80E+06 n = 2.23 E = 43.25 }
1248 B17f: C4H6 + O -> I-C4H5 + OH { A = 3.56E+14 n = -0.23 E = 28.48 }
1249 B18f: C4H6 + OH -> I-C4H5 + H2O { A = 2.17E+06 n = 2.08 E = 6.58 }
1250 B19f: C4H6 + O2 -> I-C4H5 + HO2 { A = 2.11E+13 n = .00 E = 247.28 }
1251 B20f: C4H6 + CH3 -> I-C4H5 + CH4 { A = 1.03E-01 n = 3.94 E = 39.43 }
1252 B21f: C4H6 + HO2 -> I-C4H5 + H2O2 { A = 8.31E+09 n = 0.36 E = 82.58 }
1253
1254 # From C3H6 + O (x2)
1255 # Cavallotti, Leonori, Balucani et al. 2014
1256 B22f: C4H6 + O -> CH2CHO + C2H3 { A = 1.62E+09 n = 1.25 E = 2.26 }
1257 B23f: C4H6 + O -> A-C3H4 + CH2O { A = 7.26E+10 n = 0.82 E = 7.65 }
1258
1259 # From C2H4+O2
1260 B25 : C4H6 + O2 -> A-C3H5 + CO2 + H { A = 4.90E+12 n = 0.42 E = 317.15 }
1261
1262
1263 # 1,2-Butadiene
1264 # -------------
1265
1266 B26f: D-C4H6 -> C4H6 { A = 3.00E+13 n = .00 E = 271.96 }
1267 B27f: D-C4H6 + H -> C4H6 + H { A = 2.00E+13 n = .00 E = 16.74 }
1268
1269 # HPL from Knyazev & Slagle 2001
1270 B28f: C3H3 + CH3 + M9 -> D-C4H6 + M9 { A = 2.60E+57 n =-11.94 E = 40.89
1271 Ai= 4.09E+13 ni= .00 Ei= -1.08
1272 fcA = 0.825 fctA = 1341
1273 fcb = 0.175 fctb = 60000
1274 fcc = 1.0 fctc = 9770 }
1275
1276 # Revised using C3H6+H->C2H4+CH3
1277 B29f: D-C4H6 + H -> A-C3H4 + CH3 { A = 2.67E+12 n = 0.47 E = 22.72 }
1278 # Revised using A-C3H4+H->P-C3H4+H
1279 B30f: D-C4H6 + H -> P-C3H4 + CH3 { A = 2.55E+18 n = -1.09 E = 47.84 }
1280
1281 # Revised based on C3H6+R
1282 B31f: D-C4H6 -> I-C4H5 + H { A = 1.91E+54 n =-11.28 E = 464.83 }
1283 B32f: D-C4H6 + H -> I-C4H5 + H2 { A = 1.42E+04 n = 2.82 E = 14.23 }
1284 B33f: D-C4H6 + O -> I-C4H5 + OH { A = 9.50E+04 n = 2.68 E = 15.55 }
1285 B34f: D-C4H6 + OH -> I-C4H5 + H2O { A = 9.00E+04 n = 2.59 E = 1.74 }
1286 B35f: D-C4H6 + O2 -> I-C4H5 + HO2 { A = 1.17E+12 n = 0.41 E = 162.33 }
1287 B36f: D-C4H6 + CH3 -> I-C4H5 + CH4 { A = 7.00E+13 n = .00 E = 77.40 }
1288
1289 # From A-C3H4+R
1290 B37f: D-C4H6 + M0 -> S-C4H5 + H + M0 { A = 5.38E+42 n = -6.81 E = 420.61 }
1291 B38f: D-C4H6 + H -> S-C4H5 + H2 { A = 1.16E+07 n = 2.23 E = 55.80 }
1292 B39f: D-C4H6 + OH -> S-C4H5 + H2O { A = 2.23E+04 n = 2.75 E = 9.27 }
1293 B40f: D-C4H6 + CH3 -> S-C4H5 + CH4 { A = 2.06E-01 n = 3.94 E = 51.98 }
1294
1295 # From A-C3H4 + O
1296 B41f: D-C4H6 + O -> C3H6 + CO { A = 9.63E+06 n = 2.05 E = 0.75 }
1297
1298
1299 # 2-Butyne
1300 # --------
1301
1302 B42f: S-C4H6 -> C4H6 { A = 3.00E+13 n = .00 E = 271.96 }
1303 B43f: S-C4H6 -> D-C4H6 { A = 3.00E+13 n = .00 E = 280.33 }
1304 B44f: S-C4H6 + H -> D-C4H6 + H { A = 2.00E+13 n = .00 E = 16.74 }
1305
1306 # Revised using P-C3H4+H->C2H2+CH3
1307 B45f: S-C4H6 + H -> P-C3H4 + CH3 { A = 1.39E+16 n = -0.36 E = 36.11 }
1308
1309 # Peukert, Naumann, Braun-unkhoff 2009
1310 B46f: S-C4H6 -> S-C4H5 + H { A = 3.80E+15 n = .00 E = 373.21 }
1311
1312 # Revised based on C2H6+R
1313 B47f: S-C4H6 + H -> S-C4H5 + H2 { A = 1.70E+05 n = 2.70 E = 24.02 }
1314 B48f: S-C4H6 + O -> S-C4H5 + OH { A = 3.17E+01 n = 3.80 E = 13.10 }
1315 B49f: S-C4H6 + OH -> S-C4H5 + H2O { A = 1.61E+06 n = 2.22 E = 3.10 }
1316 B50f: S-C4H6 + CH3 -> S-C4H5 + CH4 { A = 3.45E+01 n = 3.44 E = 43.47 }
1317
1318 # From C2H2 - Total rate
1319 #B51 : S-C4H6 + O -> C2H3 + CO + CH3 { A = 3.70E+09 n = 1.28 E = 10.34 }
1320 B52 : S-C4H6 + OH -> C2H4 + CO + CH3 { A = 1.86E+03 n = 2.67 E = 0.97 }
1321
1322
1323 # Butadienyl radicals
1324 # -------------------
1325
1326 B53f: C2H3 + C2H2 -> N-C4H5 { A = 9.30E+38 n = -8.76 E = 50.21 }
1327 B54f: C2H3 + C2H2 -> I-C4H5 { A = 1.60E+46 n =-10.98 E = 77.82 }
1328
1329 B55f: C2H3 + C2H3 -> I-C4H5 + H { A = 1.20E+22 n = -2.44 E = 57.13 }
1330 B56f: C2H3 + C2H3 -> N-C4H5 + H { A = 2.40E+20 n = -2.04 E = 64.28 }
1331
1332 B57f: C4H4 + H -> N-C4H5 { A = 1.30E+51 n =-11.92 E = 69.04 }
1333 B58f: C4H4 + H -> I-C4H5 { A = 4.90E+51 n =-11.92 E = 74.06 }
1334
1335 B59f: N-C4H5 -> I-C4H5 { A = 1.50E+67 n =-16.89 E = 247.27 }
1336 B60f: N-C4H5 + H -> I-C4H5 + H { A = 3.10E+26 n = -3.35 E = 72.90 }
1337
1338 B61f: N-C4H5 + H -> C4H4 + H2 { A = 1.50E+13 n = .00 E = .00 }
1339 B62f: N-C4H5 + OH -> C4H4 + H2O { A = 2.50E+12 n = .00 E = .00 }
1340 B63f: N-C4H5 + O2 -> C4H4 + HO2 { A = 6.70E+05 n = 1.61 E = -1.61 }
1341 B64f: N-C4H5 + CH3 -> C4H4 + CH4 { A = 4.52E+12 n = .00 E = -3.20 }
1342
1343 # From C2H3
1344 B66f: N-C4H5 + O -> A-C3H5 + CO { A = 1.03E+13 n = 0.21 E = -1.79 }
1345 B67 : N-C4H5 + O2 -> A-C3H5 + CO + O { A = 3.80E+11 n = 0.19 E = 0.20 }
1346 B68f: N-C4H5 + O2 -> C2H3CHO + HCO { A = 4.05E+17 n = -1.86 E = 4.88 }
1347 B69 : N-C4H5 + O2 -> C2H3CHO + CO + H { A = 2.22E+16 n = -1.35 E = 3.28 }
1348
1349 B70f: I-C4H5 + H -> C3H3 + CH3 { A = 2.00E+13 n = .00 E = 8.37 }
1350
1351 B71f: I-C4H5 + H -> C4H4 + H2 { A = 3.00E+13 n = .00 E = .00 }
1352 B72f: I-C4H5 + OH -> C4H4 + H2O { A = 5.00E+12 n = .00 E = .00 }
1353 B73f: I-C4H5 + O2 -> C4H4 + HO2 { A = 1.34E+06 n = 1.61 E = -1.61 }
1354 B74f: I-C4H5 + CH3 -> C4H4 + CH4 { A = 9.04E+12 n = .00 E = -3.20 }
1355
1356 # From A-C3H5
1357 B75f: I-C4H5 + O -> CH2CO + C2H3 { A = 3.17E+13 n = 0.03 E = -1.65 }
1358 B76 : I-C4H5 + O2 -> CH2CO + C2H2 + OH { A = 9.71E+20 n = -2.70 E = 104.52 }
1359 B77f: I-C4H5 + O2 -> CH2CO + CH2CHO { A = 3.08E+09 n = 0.37 E = 70.75 }
1360 B78 : I-C4H5 + HO2 -> CH2CO + C2H3 + OH { A = 1.19E+09 n = 1.03 E = -9.41 }
1361
1362 B79f: S-C4H5 -> I-C4H5 { A = 1.50E+67 n =-16.89 E = 247.27 }
1363 B80f: S-C4H5 + H -> I-C4H5 + H { A = 3.10E+26 n = -3.35 E = 72.90 }
1364
1365 # From C3H3
1366 #81 : S-C4H5 + O -> C3H2O + CH3 { A = 1.38E+14 n = .00 E = .00 }
1367 B82 : S-C4H5 + O2 -> CH2CO + CH3 + CO { A = 1.70E+05 n = 1.70 E = 6.28 }
1368 B83 : S-C4H5 + HO2 -> C2H2 + CH3 + CO + OH { A = 8.00E+11 n = .00 E = .00 }
1369
1370 # From C3H3+C3H3
1371 B84f: S-C4H5 + C3H3 -> A1CH3-C7H8 { A = 1.87E+46 n = -9.84 E = 70.31 }
1372 B85f: S-C4H5 + C3H3 -> A1CH3*-C7H7 + H { A = 5.77E+37 n = -7.00 E = 131.82 }
1373
1374
1375
1376 #==========================================================================#
1377 # #
1378 # "A Detailed Chemical Kinetic Reaction Mechanism for #
1379 # n-Alkane Hydrocarbons from n-Octane to n-Hexadecane" #
1380 # C. K. Westbrook, W. J. Pitz, O. Herbinet, H. J. Curran and E. J. Silke #
1381 # Combustion and Flame 156:181-199 (2009). #
1382 # #
1383 # LLNL-MI-407455 - version dated 2008-09-02 C.K. Westbrook #
1384 # #
1385 #==========================================================================#
1386
1387
1388 # ------------------- HIGH TEMPERATURE -------------------- #
1389 # ---------------------- 3 Species ------------------------ #
1390 # --------------------- 17 Reactions ---------------------- #
1391
1392 # Reactions of N-C6H14
1393
1394 HX01 : N-C6H14 -> N-C5H11 + CH3 { A = 6.03E+18 n = -0.67 E = 362.13 }
1395 HX02 : N-C6H14 -> N-C4H9 + C2H5 { A = 1.62E+22 n = -1.49 E = 364.80 }
1396 HX03 : N-C6H14 -> N-C3H7 + N-C3H7 { A = 2.62e+22 n = -1.56 E = 367.94 }
1397
1398 HX04 : N-C6H14 + H -> C6H13 + H2 { A = 6.16E+07 n = 2.10 E = 22.91 }
1399 HX05 : N-C6H14 + O -> C6H13 + OH { A = 1.42E+06 n = 2.56 E = 12.62 }
1400 HX06 : N-C6H14 + OH -> C6H13 + H2O { A = 7.49E+06 n = 2.09 E = -2.61 }
1401 HX07 : N-C6H14 + O2 -> C6H13 + HO2 { A = 1.70E+13 n = 0.20 E = 209.99 }
1402 HX08 : N-C6H14 + HO2 -> C6H13 + H2O2 { A = 6.27E+12 n = 0.21 E = 74.05 }
1403
1404 # Reactions of C6H13 (lumped)
1405 # Branching ratios 0.2/0.4
1406
1407 HX09 : C6H13 -> N-C4H9 + C2H4 { A = 3.20E+12 n = 0.13 E = 120.84 }
1408 HX10 : C6H13 -> N-C3H7 + C3H6 { A = 5.52E+12 n = 0.17 E = 125.16 }
1409 HX11 : C6H13 -> C2H5 + C4H8 { A = 2.76E+12 n = 0.17 E = 125.16 }
1410 HX12 : C6H13 -> CH3 + C5H10 { A = 2.76E+12 n = 0.17 E = 125.16 }
1411
1412 HX13 : C6H13 -> C6H12 + H { A = 1.78E+08 n = 1.63 E = 144.24 }
1413
1414 HX14 : C6H13 + HO2 -> C6H13O + OH { A = 7.00E+12 n = .00 E = -4.18 }
1415 HX15 : C6H13 + CH3O2 -> C6H13O + CH3O { A = 7.00E+12 n = .00 E = -4.18 }
1416
1417 # Reactions of C6H13O
1418
1419 HX16 : C6H13O -> N-C5H11 + CH2O { A = 1.19E+18 n = -1.50 E = 84.44 }
1420 HX17 : C6H13O -> N-C4H9 + CH3CHO { A = 7.16E+22 n = -2.78 E = 96.22 }
1421 HX18 : C6H13O -> N-C3H7 + C2H5 + HCO { A = 4.10E+17 n = -1.31 E = 81.60 }
1422
1423
1424
1425 # ------------------- LOW TEMPERATURE -------------------- #
1426 # ---------------------- 5 Species ----------------------- #
1427 # -------------------- 11 Reactions ---------------------- #
1428
1429 /* Commented for now */
1430
1431 # Formation of ROO
1432
1433 HX20 : C6H13 + O2 -> C6H13O2 { A = 1.36E+13 n = -0.08 E = 0.87 }
1434 HX21 : C6H13O2 -> C6H13 + O2 { A = 1.71E+23 n = -2.33 E = 158.32 }
1435 HX22 : C6H13O2 -> C6H12OOH { A = 1.83E+05 n = 1.70 E = 80.90 }
1436
1437 # Reactions of QOOH
1438
1439 HX23 : C6H12OOH -> C6H13O2 { A = 7.53E+04 n = 1.25 E = 24.89 }
1440 HX24 : C6H12OOH -> C6H12 + HO2 { A = 4.01E+00 n = 3.28 E = 53.36 }
1441 HX25 : C6H12OOH -> C6H12O + OH { A = 1.33E+12 n = -0.74 E = 42.56 }
1442 HX26 : C6H12OOH + O2 -> C6H13O4 { A = 7.71E+12 n = -0.01 E = -0.06 }
1443
1444 # Reactions of O2QOOH
1445
1446 HX27 : C6H13O4 -> C6H12OOH + O2 { A = 2.31E+21 n = -1.97 E = 153.05 }
1447 HX28 : C6H13O4 -> OC6H11OOH + OH { A = 6.47E+09 n = 0.18 E = 83.01 }
1448
1449 # Reactions of OQ'OOH
1450 # all products lumped
1451
1452 HX29: OC6H11OOH -> C5H10 + CH2CO + OH { A = 3.26E+09 n = 1.93 E = 161.11 }
1453
1454 # Reactions of QO
1455 # all products lumped
1456
1457 HX30: C6H12O + OH -> N-C4H9 + CH2CO + H2O { A = 3.68E+12 n = .00 E = .00 }
1458 /**/
1459
1460
1461 #==========================================================================#
1462 # #
1463 # "A Comprehensive Modeling Study of n-Heptane Oxidation" #
1464 # Curran, H. J., Gaffuri, P., Pitz, W. J., and Westbrook, C. K. #
1465 # Combustion and Flame 114:149-177 (1998). #
1466 # #
1467 # UCRL-WEB-204236 - Review and release date: May 19, 2004. #
1468 # #
1469 #==========================================================================#
1470
1471
1472 # ------------------- HIGH TEMPERATURE -------------------- #
1473 # ---------------------- 3 Species ------------------------ #
1474 # --------------------- 19 Reactions ---------------------- #
1475
1476 # Reactions of N-C7H16
1477
1478 # Rates from LLNL
1479 # Multiplied by 3 to match overall decomp rate from exp
1480 # (Davidson, Oehlschlaeger, Hanson 2007)
1481 HP01 : N-C7H16 -> N-C6H13 + CH3 { A = 8.79E+73 n =-16.61 E = 497.48 }
1482 HP02 : N-C7H16 -> N-C5H11 + C2H5 { A = 2.43E+78 n =-17.62 E = 503.75 }
1483 HP03 : N-C7H16 -> N-C4H9 + N-C3H7 { A = 4.26E+78 n =-17.71 E = 505.01 }
1484
1485 HP04 : N-C7H16 + H -> C7H15 + H2 { A = 9.90E+07 n = 2.06 E = 22.98 }
1486 HP05 : N-C7H16 + O -> C7H15 + OH { A = 1.72E+05 n = 2.81 E = 9.46 }
1487 HP06 : N-C7H16 + OH -> C7H15 + H2O { A = 9.68E+06 n = 2.08 E = -2.73 }
1488 HP07 : N-C7H16 + O2 -> C7H15 + HO2 { A = 2.89E+13 n = 0.20 E = 209.66 }
1489 HP08 : N-C7H16 + HO2 -> C7H15 + H2O2 { A = 7.57E+12 n = 0.21 E = 73.78 }
1490
1491 # Reactions of C7H15 (lumped)
1492 # Branching ratios 0.17/0.33/0.17
1493 # NEW Branching ratios from OH rate about the same at 1000K
1494
1495 HP09 : C7H15 -> N-C5H11 + C2H4 { A = 2.72E+12 n = 0.13 E = 120.84 }
1496 HP10 : C7H15 -> N-C4H9 + C3H6 { A = 4.55E+12 n = 0.17 E = 125.16 }
1497 HP11 : C7H15 -> N-C3H7 + C4H8 { A = 2.28E+12 n = 0.17 E = 125.16 }
1498 HP12 : C7H15 -> C2H5 + C5H10 { A = 2.35E+12 n = 0.17 E = 125.16 }
1499 HP13 : C7H15 -> CH3 + C6H12 { A = 2.28E+12 n = 0.17 E = 125.16 }
1500
1501 HP14 : C7H15 -> C7H14 + H { A = 1.78E+08 n = 1.63 E = 144.24 }
1502
1503 HP15 : C7H15 + HO2 -> C7H15O + OH { A = 7.00E+12 n = .00 E = -4.18 }
1504 HP16 : C7H15 + CH3O2 -> C7H15O + CH3O { A = 7.00E+12 n = .00 E = -4.18 }
1505
1506 # Reactions of C7H15O (lumped)
1507
1508 HP17 : C7H15O -> N-C5H11 + CH3CHO { A = 8.92E+19 n = -2.03 E = 87.88 }
1509 HP18 : C7H15O -> N-C4H9 + C2H5 + HCO { A = 2.23E+15 n = -0.70 E = 77.85 }
1510 HP19 : C7H15O -> N-C3H7 + N-C3H7 + HCO { A = 6.18E+16 n = -1.36 E = 77.48 }
1511
1512
1513 # ------------------- LOW TEMPERATURE -------------------- #
1514 # ---------------------- 5 Species ----------------------- #
1515 # -------------------- 11 Reactions ---------------------- #
1516
1517 /* Commented for now */
1518
1519 # Formation of ROO
1520
1521 HP20: C7H15 + O2 -> C7H15O2 { A = 1.68E+13 n = -0.11 E = 1.01 }
1522 HP21: C7H15O2 -> C7H15 + O2 { A = 1.92E+22 n = -2.11 E = 156.08 }
1523 HP22: C7H15O2 -> C7H14OOH { A = 1.88E+05 n = 1.68 E = 79.51 }
1524
1525 # Reactions of QOOH
1526
1527 HP23: C7H14OOH -> C7H15O2 { A = 7.64E+05 n = 0.91 E = 25.45 }
1528 HP24: C7H14OOH -> C7H14 + HO2 { A = 5.85E+03 n = 2.40 E = 64.08 }
1529 HP25: C7H14OOH -> C7H14O + OH { A = 3.97E-10 n = 5.69 E = 1.57 }
1530 HP26: C7H14OOH + O2 -> C7H15O4 { A = 1.51E+13 n = -0.09 E = 0.53 }
1531
1532 # Reactions of O2QOOH
1533
1534 HP27: C7H15O4 -> C7H14OOH + O2 { A = 1.71E+22 n = -2.13 E = 155.32 }
1535 HP28: C7H15O4 -> OC7H13OOH + OH { A = 4.25E+10 n = -0.11 E = 81.48 }
1536
1537 # Reactions of OQ'OOH
1538 # all products lumped
1539
1540 HP29: OC7H13OOH -> N-C3H7 + CH3CHO + CH2CO + OH { A = 3.26E+09 n = 1.93 E = 161.11 }
1541
1542 # Reactions of QO
1543 # all products lumped
1544
1545 HP30: C7H14O + OH -> N-C5H11 + CH2CO + H2O { A = 3.68E+12 n = .00 E = .00 }
1546 /**/
1547
1548
1549
1550 #==========================================================================#
1551 # #
1552 # "A Detailed Chemical Kinetic Reaction Mechanism for #
1553 # n-Alkane Hydrocarbons from n-Octane to n-Hexadecane" #
1554 # C. K. Westbrook, W. J. Pitz, O. Herbinet, H. J. Curran and E. J. Silke #
1555 # Combustion and Flame 156:181-199 (2009). #
1556 # #
1557 # LLNL-MI-407455 - version dated 2008-09-02 C.K. Westbrook #
1558 # #
1559 #==========================================================================#
1560
1561
1562 # H-abs by H from Cartensen & Dean 2009
1563 # H-abs by OH from Kwok & Atkinson 1995 / Pang, Hanson et al. 2011
1564 # Total decomp rate fitted to McDonald 2012 and Klingbeil et al. 2008
1565 # -> individual rates rescaled with same branching ratios
1566
1567 # ------------------- HIGH TEMPERATURE -------------------- #
1568 # ---------------------- 3 Species ------------------------ #
1569 # --------------------- 73 Reactions ---------------------- #
1570
1571 # Reactions of N-C12H26
1572
1573 DD01 : N-C12H26 -> N-C10H21 + C2H5 { A = 1.68E+24 n = -2.11 E = 368.84 }
1574 DD02 : N-C12H26 -> N-C9H19 + N-C3H7 { A = 2.46E+24 n = -2.12 E = 371.27 }
1575 DD03 : N-C12H26 -> N-C8H17 + N-C4H9 { A = 1.21E+24 n = -2.07 E = 369.64 }
1576 DD04 : N-C12H26 -> N-C7H15 + N-C5H11 { A = 1.13E+24 n = -2.06 E = 369.58 }
1577 DD05 : N-C12H26 -> N-C6H13 + N-C6H13 { A = 2.59E+24 n = -2.12 E = 369.69 }
1578
1579 DD06 : N-C12H26 + H -> C12H25 + H2 { A = 3.59E+08 n = 1.97 E = 23.16 }
1580 DD07 : N-C12H26 + O -> C12H25 + OH { A = 3.97E+05 n = 2.76 E = 9.19 }
1581 DD08 : N-C12H26 + OH -> C12H25 + H2O { A = 2.18E+07 n = 2.05 E = -2.95 }
1582 DD09 : N-C12H26 + O2 -> C12H25 + HO2 { A = 1.05E+14 n = 0.10 E = 209.77 }
1583 DD10 : N-C12H26 + HO2 -> C12H25 + H2O2 { A = 2.86E+13 n = 0.11 E = 73.93 }
1584
1585 # Reactions of C12H25 (lumped)
1586 # Branching ratios 0.09/.18
1587 # NEW Branching ratios from OH rate about same at 1000K
1588
1589 DD11 : C12H25 -> N-C10H21 + C2H4 { A = 1.44E+12 n = 0.13 E = 120.84 }
1590 DD12 : C12H25 -> N-C9H19 + C3H6 { A = 2.48E+12 n = 0.17 E = 125.16 }
1591 DD13 : C12H25 -> N-C8H17 + C4H8 { A = 2.48E+12 n = 0.17 E = 125.16 }
1592 DD14 : C12H25 -> N-C7H15 + C5H10 { A = 1.24E+12 n = 0.17 E = 125.16 }
1593 DD15 : C12H25 -> N-C6H13 + C6H12 { A = 1.24E+12 n = 0.17 E = 125.16 }
1594 DD16 : C12H25 -> N-C5H11 + C7H14 { A = 1.24E+13 n = 0.17 E = 125.16 }
1595 DD17 : C12H25 -> N-C4H9 + C8H16 { A = 1.24E+13 n = 0.17 E = 125.16 }
1596 DD18 : C12H25 -> N-C3H7 + C9H18 { A = 1.24E+12 n = 0.17 E = 125.16 }
1597 DD19 : C12H25 -> C2H5 + C10H20 { A = 1.24E+12 n = 0.17 E = 125.16 }
1598
1599 DD20 : C12H25 -> C12H24 + H { A = 1.78E+08 n = 1.63 E = 144.24 }
1600
1601 DD21 : C12H25 + HO2 -> C12H25O + OH { A = 7.00E+12 n = .00 E = -4.18 }
1602 DD22 : C12H25 + CH3O2 -> C12H25O + CH3O { A = 7.00E+12 n = .00 E = -4.18 }
1603
1604 # Reactions of C12H25O
1605
1606 DD23 : C12H25O -> N-C10H21 + CH3CHO { A = 4.35E+08 n = 1.31 E = 64.79 }
1607 DD24 : C12H25O -> N-C9H19 + C2H5 + HCO { A = 8.37E+18 n = -1.84 E = 82.98 }
1608 DD25 : C12H25O -> N-C8H17 + N-C3H7 + HCO { A = 9.83E+44 n = -9.70 E = 134.38 }
1609 DD26 : C12H25O -> N-C7H15 + N-C4H9 + HCO { A = 8.35E+61 n =-14.50 E = 179.77 }
1610 DD27 : C12H25O -> N-C6H13 + N-C5H11 + HCO { A = 4.63E+64 n =-15.38 E = 182.82 }
1611
1612 # Reactions of C12H24 (lumped)
1613
1614 DD28 : C12H24 -> N-C9H19 + A-C3H5 { A = 9.53E+15 n = -0.18 E = 298.01 }
1615 DD32 : C12H24 -> N-C8H17 + C4H7 { A = 1.87E+15 n = 0.04 E = 296.85 }
1616 DD31 : C12H24 -> N-C7H15 + C5H9 { A = 1.50E+15 n = -0.02 E = 297.10 }
1617 DD30 : C12H24 -> N-C5H11 + C7H13 { A = 2.08E+15 n = -0.04 E = 297.23 }
1618 DD29 : C12H24 -> N-C4H9 + C8H15 { A = 1.51E+13 n = 0.52 E = 294.52 }
1619
1620 DD33 : C12H24 + H -> C12H23 + H2 { A = 3.70E+13 n = .00 E = 16.32 }
1621 DD34 : C12H24 + OH -> C12H23 + H2O { A = 3.00E+13 n = .00 E = 5.15 }
1622
1623 # Reactions of C12H23 (lumped)
1624
1625 DD35 : C12H23 -> C10H19 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1626 DD36 : C12H23 -> C9H17 + C3H6 { A = 1.38E+13 n = 0.17 E = 125.16 }
1627 DD37 : C12H23 -> C8H15 + C4H8 { A = 1.38E+13 n = 0.17 E = 125.16 }
1628 DD38 : C12H23 -> C7H13 + C5H10 { A = 1.38E+13 n = 0.17 E = 125.16 }
1629 DD39 : C12H23 -> C5H9 + C7H14 { A = 1.38E+13 n = 0.17 E = 125.16 }
1630 DD40 : C12H23 -> C4H7 + C8H16 { A = 1.38E+13 n = 0.17 E = 125.16 }
1631 DD41 : C12H23 -> A-C3H5 + C9H18 { A = 1.38E+13 n = 0.17 E = 125.16 }
1632 DD42 : C12H23 -> C2H3 + C10H20 { A = 1.38E+13 n = 0.17 E = 125.16 }
1633
1634
1635
1636
1637 # -------------------- LOW TEMPERATURE -------------------- #
1638 # ----------------------- 10 Species ---------------------- #
1639 # ---------------------- 21 Reactions --------------------- #
1640 /**/
1641 # Reactions of C12H25O2
1642 # Backward rate reduced (x1/6)
1643 # to mimic lumping of peroxy species
1644
1645 DD50 : C12H25 + O2 -> C12H25O2 { A = 9.52E+12 n = -0.04 E = 0.23 }
1646 DD51 : C12H25O2 -> C12H25 + O2 { A = 1.52E+22 n = -2.31 E = 156.59 }
1647 DD52 : C12H25O2 -> C12H24OOH { A = 1.13E+06 n = 1.46 E = 80.17 }
1648 DD53 : C12H24OOH -> C12H25O2 { A = 4.47E+21 n = -3.86 E = 58.11 }
1649
1650 # Reactions of C12H24OOH
1651
1652 DD54 : C12H24OOH -> C12H24 + HO2 { A = 2.21E+14 n = -0.81 E = 84.74 }
1653 DD55 : C12H24OOH -> C12H24O + OH { A = 3.25E-11 n = 5.92 E = -7.84 }
1654 DD56 : C12H24OOH + O2 -> C12H25O4 { A = 1.32E+13 n = -0.08 E = 0.47 }
1655
1656 # Reactions of C12H25O4
1657
1658 DD57 : C12H25O4 -> C12H24OOH + O2 { A = 1.92E+23 n = -2.42 E = 157.60 }
1659 DD58 : C12H25O4 -> C12H24O3 + OH { A = 1.28E+07 n = 0.89 E = 72.18 }
1660
1661 # Reactions of C12H24O3
1662 # lump all decomposition pathways
1663
1664 DD59 : C12H24O3 -> N-C8H17 + CH3CHO + CH2CO + OH{ A = 8.95E+14 n = 0.32 E = 171.10 }
1665
1666 # Reactions of C12H24O
1667 # lump all decomposition pathways
1668
1669 DD60 : C12H24O + OH -> N-C8H17 + C2H4 + CH2CO + H2O{ A = 3.09E+13 n = -0.27 E = 1.61 }
1670
1671 # Reactions of C8H17O2
1672
1673 DD61 : N-C8H17 + O2 -> C8H17O2 { A = 1.65E+22 n = -2.85 E = 19.78 }
1674 DD62 : C8H17O2 -> N-C8H17 + O2 { A = 2.48E+21 n = -1.94 E = 150.73 }
1675 DD63 : C8H17O2 -> C8H16OOH { A = 1.11E+06 n = 1.40 E = 79.77 }
1676
1677 # Reactions of C8H16OOH
1678
1679 DD64 : C8H16OOH -> C8H16O + OH { A = 3.07E+02 n = 2.15 E = 24.57 }
1680 DD65 : C8H16OOH -> C8H16 + HO2 { A = 5.11E+06 n = 1.40 E = 70.08 }
1681 DD66 : C8H16OOH + O2 -> C8H17O4 { A = 1.16E+11 n = 0.53 E = -3.58 }
1682
1683 # Reactions of C8H17O4/C8H16O3
1684
1685 DD67 : C8H17O4 -> C8H16OOH + O2 { A = 1.37E+23 n = -2.37 E = 157.49 }
1686 DD68 : C8H17O4 -> C8H16O3 + OH { A = 9.98E+06 n = 1.02 E = 83.92 }
1687 DD69 : C8H16O3 -> N-C4H9 + CH3CHO + CH2CO + OH { A = 4.44E+32 n = -4.98 E = 207.98 }
1688
1689 DD70 : C8H16O + OH -> N-C6H13 + CH2CO + H2O { A = 3.09E+13 n = -0.27 E = 1.61 }
1690 /**/
1691
1692
1693
1694 #==========================================================================#
1695 # #
1696 # Additional n-alkyl mechanism #
1697 # (based on) #
1698 # Lawrence Livermore n-Alkanes Mechanism - ver 2 #
1699 # #
1700 #==========================================================================#
1701
1702
1703 # ------------------- HIGH TEMPERATURE -------------------- #
1704 # ---------------------- 21 Species ----------------------- #
1705 # --------------------- 70 Reactions ---------------------- #
1706
1707 # H-abstractions from Miller & Klippenstein 2013 - HPL
1708 # p -> { A = 1.78E+08 n = 1.63 E = 144.24 }
1709 # Beta scissions from Ratkiewicz & Truong 2012 - HPL
1710 # p -> { A = 1.60E+13 n = 0.13 E = 120.84 }
1711 # st -> { A = 1.38E+13 n = 0.17 E = 125.16 }
1712 # H-abstraction for alkane from Cartensen & Dean 2009
1713 # p -> { A = 1.40E+07 n = 1.97 E = 34.31 }
1714 # s -> { A = 3.80E+07 n = 1.86 E = 23.43 }
1715 # N-alkene decomposition from Manion & Awan 2015
1716 # { A = 3.39E+15 n = .00 E = 302.40 }
1717
1718
1719 # Decyl radical
1720 # -------------
1721
1722 # Reactions of N-C10H21
1723
1724 NC01 : N-C10H21 -> N-C8H17 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1725 NC02 : N-C10H21 -> C10H20 + H { A = 2.04E+10 n = 0.95 E = 141.45 }
1726
1727 # Reactions of C10H20
1728
1729 NC03 : C10H20 -> N-C7H15 + A-C3H5 { A = 3.39E+15 n = .00 E = 302.40 }
1730
1731 NC04 : C10H20 + H -> C10H19 + H2 { A = 3.70E+13 n = .00 E = 16.32 }
1732 NC05 : C10H20 + OH -> C10H19 + H2O { A = 3.00E+13 n = .00 E = 5.15 }
1733
1734 # Reactions of C10H19 (lumped)
1735
1736 NC06 : C10H19 -> C8H15 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1737 NC07 : C10H19 -> C7H13 + C3H6 { A = 1.38E+13 n = 0.17 E = 125.16 }
1738 NC08 : C10H19 -> C6H11 + C4H8 { A = 1.38E+13 n = 0.17 E = 125.16 }
1739 NC09 : C10H19 -> C5H9 + C5H10 { A = 1.38E+13 n = 0.17 E = 125.16 }
1740 NC10 : C10H19 -> C4H7 + C6H12 { A = 1.38E+13 n = 0.17 E = 125.16 }
1741 NC11 : C10H19 -> A-C3H5 + C7H14 { A = 1.38E+13 n = 0.17 E = 125.16 }
1742 NC12 : C10H19 -> C2H3 + C8H16 { A = 1.38E+13 n = 0.17 E = 125.16 }
1743
1744
1745 # Nonyl radical
1746 # -------------
1747
1748 # Reactions of N-C9H19
1749
1750 NC13 : N-C9H19 -> N-C7H15 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1751 NC14 : N-C9H19 -> C9H18 + H { A = 2.04E+10 n = 0.95 E = 141.45 }
1752
1753 # Reactions of C9H18
1754
1755 NC15 : C9H18 -> N-C6H13 + A-C3H5 { A = 3.39E+15 n = .00 E = 302.40 }
1756
1757 NC16 : C9H18 + H -> C9H17 + H2 { A = 3.70E+13 n = .00 E = 16.32 }
1758 NC17 : C9H18 + OH -> C9H17 + H2O { A = 3.00E+13 n = .00 E = 5.15 }
1759
1760 # Reactions of C9H17 (lumped)
1761
1762 NC18 : C9H17 -> C7H13 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1763 NC19 : C9H17 -> C6H11 + C3H6 { A = 1.38E+13 n = 0.17 E = 125.16 }
1764 NC20 : C9H17 -> C5H9 + C4H8 { A = 1.38E+13 n = 0.17 E = 125.16 }
1765 NC21 : C9H17 -> C4H7 + C5H10 { A = 1.38E+13 n = 0.17 E = 125.16 }
1766 NC22 : C9H17 -> A-C3H5 + C6H12 { A = 1.38E+13 n = 0.17 E = 125.16 }
1767 NC23 : C9H17 -> C2H3 + C7H14 { A = 1.38E+13 n = 0.17 E = 125.16 }
1768
1769
1770 # Octyl radical
1771 # -------------
1772
1773 # Reactions of N-C8H17
1774
1775 NC24 : N-C8H17 -> N-C6H13 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1776 NC25 : N-C8H17 -> C8H16 + H { A = 2.04E+10 n = 0.95 E = 141.45 }
1777
1778 # Reactions of C8H16
1779
1780 NC26 : C8H16 -> N-C5H11 + A-C3H5 { A = 3.39E+15 n = .00 E = 302.40 }
1781
1782 NC27 : C8H16 + H -> C8H15 + H2 { A = 3.70E+13 n = .00 E = 16.32 }
1783 NC28 : C8H16 + OH -> C8H15 + H2O { A = 3.00E+13 n = .00 E = 5.15 }
1784
1785 # Reactions of C8H15 (lumped)
1786
1787 NC29 : C8H15 -> C6H11 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1788 NC30 : C8H15 -> C5H9 + C3H6 { A = 1.38E+13 n = 0.17 E = 125.16 }
1789 NC31 : C8H15 -> C4H7 + C4H8 { A = 1.38E+13 n = 0.17 E = 125.16 }
1790 NC32 : C8H15 -> A-C3H5 + C5H10 { A = 1.38E+13 n = 0.17 E = 125.16 }
1791 NC33 : C8H15 -> C2H3 + C6H12 { A = 1.38E+13 n = 0.17 E = 125.16 }
1792
1793
1794 # Heptyl radical
1795 # --------------
1796
1797 # Reactions of N-C7H15
1798
1799 NC34 : N-C7H15 -> N-C5H11 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1800 NC35 : N-C7H15 -> C7H14 + H { A = 2.04E+10 n = 0.95 E = 141.45 }
1801
1802 # Reactions of C7H14
1803
1804 NC36 : C7H14 -> N-C4H9 + A-C3H5 { A = 3.39E+15 n = .00 E = 302.40 }
1805
1806 NC37 : C7H14 + H -> C7H13 + H2 { A = 3.70E+13 n = .00 E = 16.32 }
1807 NC38 : C7H14 + OH -> C7H13 + H2O { A = 3.00E+13 n = .00 E = 5.15 }
1808
1809 # Reactions of C7H13 (lumped)
1810
1811 NC39 : C7H13 -> C5H9 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1812 NC40 : C7H13 -> C4H7 + C3H6 { A = 1.38E+13 n = 0.17 E = 125.16 }
1813 NC41 : C7H13 -> A-C3H5 + C4H8 { A = 1.38E+13 n = 0.17 E = 125.16 }
1814 NC42 : C7H13 -> C2H3 + C5H10 { A = 1.38E+13 n = 0.17 E = 125.16 }
1815
1816
1817 # Hexyl radical
1818 # -------------
1819
1820 # Reactions of N-C6H13
1821
1822 NC43 : N-C6H13 -> N-C4H9 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1823 NC44 : N-C6H13 -> C6H12 + H { A = 2.04E+10 n = 0.95 E = 141.45 }
1824
1825 # Reactions of C6H12
1826
1827 NC45 : C6H12 -> N-C3H7 + A-C3H5 { A = 8.52E+26 n = -3.39 E = 320.10 }
1828
1829 NC46 : C6H12 + H -> C6H11 + H2 { A = 3.70E+13 n = .00 E = 16.32 }
1830 NC47 : C6H12 + OH -> C6H11 + H2O { A = 3.00E+13 n = .00 E = 5.15 }
1831
1832 # Reactions of C6H11 (lumped)
1833
1834 NC48 : C6H11 -> C4H7 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1835 NC49 : C6H11 -> A-C3H5 + C3H6 { A = 1.38E+13 n = 0.17 E = 125.16 }
1836 NC50 : C6H11 -> C2H3 + C4H8 { A = 1.38E+13 n = 0.17 E = 125.16 }
1837
1838
1839 # Pentyl radical
1840 # --------------
1841
1842 # Reactions of N-C5H11
1843
1844 NC51 : N-C5H11 -> N-C3H7 + C2H4 { A = 3.24E+12 n = 0.32 E = 120.53 }
1845 NC52 : N-C5H11 -> C3H6 + C2H5 { A = 1.15E+01 n = 3.03 E = 64.07 }
1846 NC53 : N-C5H11 -> C5H10 + H { A = 2.04E+10 n = 0.95 E = 141.45 }
1847
1848 # Reactions of C5H10
1849
1850 NC54 : C5H10 -> A-C3H5 + C2H5 { A = 3.39E+15 n = .00 E = 302.40 }
1851
1852 NC55 : C5H10 + H -> C5H9 + H2 { A = 3.70E+13 n = .00 E = 16.32 }
1853 NC56 : C5H10 + OH -> C5H9 + H2O { A = 3.00E+13 n = .00 E = 5.15 }
1854
1855 # Reactions of C5H9 (lumped)
1856
1857 NC57 : C5H9 -> A-C3H5 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1858 NC58 : C5H9 -> C2H3 + C3H6 { A = 1.38E+13 n = 0.17 E = 125.16 }
1859
1860
1861 # Butyl radical
1862 # -------------
1863
1864 # Reactions of N-C4H9
1865
1866 NC59 : N-C4H9 -> C2H5 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1867 NC60 : N-C4H9 -> C4H8 + H { A = 2.04E+10 n = 0.95 E = 141.45 }
1868
1869 # Reactions of C4H8 reactions
1870
1871 # Manion, Awan 2015
1872 NC61 : C4H8 -> A-C3H5 + CH3 { A = 3.39E+15 n = .00 E = 302.40 }
1873 NC62 : C4H8 + H -> C3H6 + CH3 { A = 1.05E+09 n = 1.40 E = 3.04 }
1874 NC63 : C4H8 + H -> C2H5 + C2H4 { A = 9.02E+08 n = 1.40 E = 9.66 }
1875
1876 NC64 : C4H8 + H -> C4H7 + H2 { A = 3.70E+13 n = .00 E = 16.32 }
1877 NC65 : C4H8 + OH -> C4H7 + H2O { A = 3.00E+13 n = .00 E = 5.15 }
1878
1879 # Reactions of C4H7
1880
1881 NC66 : C4H7 -> C2H4 + C2H3 { A = 1.00E+11 n = .00 E = 154.81 }
1882 NC67 : C4H7 -> C4H6 + H { A = 1.20E+14 n = .00 E = 206.27 }
1883
1884 NC68 : C4H7 + H -> C4H6 + H2 { A = 3.16E+13 n = .00 E = .00 }
1885 NC69 : C4H7 + O2 -> C4H6 + HO2 { A = 1.00E+09 n = .00 E = .00 }
1886 NC70 : C4H7 + CH3 -> C4H6 + CH4 { A = 8.00E+12 n = .00 E = .00 }
1887
1888 NC71 : C4H7 + HO2 -> A-C3H5 + CH2O + OH { A = 7.00E+12 n = .00 E = -4.18 }
1889 NC72 : C4H7 + CH3O2 -> A-C3H5 + CH2O + CH3O { A = 7.00E+12 n = .00 E = -4.18 }
1890
1891
1892
1893
1894 #==========================================================================#
1895 # #
1896 # M. Mehl, H. J. Curran, W. J. Pitz, and C. K. Westbrook, 2009 #
1897 # LLNL-MI-421507 - Review and release date: December 16, 2009 #
1898 # #
1899 #==========================================================================#
1900
1901
1902 # ------------------- HIGH TEMPERATURE -------------------- #
1903 # ---------------------- 15 Species ----------------------- #
1904 # --------------------- 73 Reactions ---------------------- #
1905
1906 # Reactions of I-C8H18
1907
1908 IC00 : I-C8H18 -> Y-C7H15 + CH3 { A = 6.18E+25 n = -2.46 E = 350.24 }
1909 IC01 : I-C8H18 -> T-C4H8 + I-C3H7 + CH3 { A = 2.46E+23 n = -2.01 E = 348.95 }
1910 IC02 : I-C8H18 -> 2 T-C4H9 { A = 7.83E+29 n = -3.93 E = 352.08 }
1911
1912 IC03 : I-C8H18 + H -> C-C8H17 + H2 { A = 9.08E+00 n = 4.12 E = 7.45 }
1913 IC04 : I-C8H18 + O -> C-C8H17 + OH { A = 4.69E+03 n = 3.19 E = 4.52 }
1914 IC05 : I-C8H18 + OH -> C-C8H17 + H2O { A = 2.70E+05 n = 2.43 E = -4.04 }
1915 IC06 : I-C8H18 + O2 -> C-C8H17 + HO2 { A = 1.03E+11 n = 0.84 E = 196.29 }
1916 IC07 : I-C8H18 + CH3 -> C-C8H17 + CH4 { A = 1.14E-18 n = 9.25 E = -8.89 }
1917 IC08 : I-C8H18 + HO2 -> C-C8H17 + H2O2 { A = 9.85E+10 n = 0.73 E = 70.89 }
1918 IC09 : I-C8H18 + CH3O2 -> C-C8H17 + CH3O + OH { A = 9.85E+10 n = 0.73 E = 70.89 }
1919
1920 # Reactions of C-C8H17
1921
1922 IC10 : C-C8H17 -> Y-C7H14 + CH3 { A = 2.55E+39 n = -7.47 E = 189.48 }
1923 IC11 : C-C8H17 -> T-C4H9 + T-C4H8 { A = 4.28E+22 n = -2.81 E = 127.70 }
1924 IC12 : C-C8H17 -> T-C4H8 + CH3 + C3H6 { A = 4.22E+24 n = -3.34 E = 158.66 }
1925
1926 IC13 : C-C8H17 + HO2 -> D-C8H17O + OH { A = 7.00E+12 n = .00 E = -4.18 }
1927 IC14 : C-C8H17 + CH3O2 -> D-C8H17O + CH3O { A = 7.00E+12 n = .00 E = -4.18 }
1928
1929 # Reactions of D-C8H17O
1930
1931 IC15 : D-C8H17O -> T-C4H8 + CH3 + CH3COCH3 { A = 1.33E+23 n = -2.98 E = 64.44 }
1932 IC16 : D-C8H17O -> T-C4H9 + I-C3H7 + HCO { A = 7.95E+33 n = -6.00 E = 97.57 }
1933 IC17 : D-C8H17O -> Y-C7H15 + CH2O { A = 2.69E+20 n = -2.08 E = 62.99 }
1934
1935 # Reactions of Y-C7H15
1936
1937 IC18 : Y-C7H15 -> T-C4H9 + C3H6 { A = 5.14E+23 n = -2.93 E = 131.78 }
1938 IC19 : Y-C7H15 -> T-C4H8 + I-C3H7 { A = 5.87E+21 n = -2.57 E = 136.80 }
1939 IC20 : Y-C7H15 -> Y-C7H14 + H { A = 6.13E+13 n = 0.03 E = 153.44 }
1940
1941 # Reactions of Y-C7H14
1942
1943 IC21 : Y-C7H14 -> T-C4H9 + A-C3H5 { A = 3.98E+26 n = -3.48 E = 320.14 }
1944 IC22 : Y-C7H14 -> T-C4H7 + I-C3H7 { A = 5.29E+24 n = -2.55 E = 317.38 }
1945
1946 IC23 : Y-C7H14 + H -> X-C7H13 + H2 { A = 2.38E-13 n = 7.67 E = -47.65 }
1947 IC24 : Y-C7H14 + OH -> X-C7H13 + H2O { A = 6.46E-09 n = 6.18 E = -41.33 }
1948
1949 # Reactions of X-C7H13
1950
1951 IC25 : X-C7H13 -> T-C4H9 + A-C3H4 { A = 8.71E+21 n = -2.43 E = 249.07 }
1952 IC26 : X-C7H13 -> T-C4H8 + T-C3H5 { A = 6.32E+18 n = -1.80 E = 182.42 }
1953 IC27 : X-C7H13 -> T-C4H7 + C3H6 { A = 2.10E+16 n = -1.09 E = 74.56 }
1954
1955 #C28 : X-C7H13 + HO2 -> I-C3H5CHO + I-C3H7 + OH { A = 1.00E+13 n = .00 E = .00 }
1956
1957 # Reactions of T-C4H9
1958
1959 # Ratkeiwicz 2011 (x0.5 for lumping)
1960 IC29 : T-C4H9 -> C3H6 + CH3 { A = 3.30E+12 n = 0.37 E = 128.58 }
1961
1962 IC30 : T-C4H9 -> T-C4H8 + H { A = 5.35E+10 n = 1.06 E = 137.99 }
1963
1964 #C31 : T-C4H9 + HO2 -> T-C4H9O + OH { A = 7.00E+12 n = .00 E = -4.18 }
1965 #C32 : T-C4H9 + CH3O2 -> T-C4H9O + CH3O { A = 7.00E+12 n = .00 E = -4.18 }
1966
1967 # Reactions of T-C4H9O
1968
1969 #C33 : T-C4H9O -> I-C3H7 + HCO + H { A = 1.78E+39 n = -7.30 E = 156.05 }
1970 #C34 : T-C4H9O -> I-C3H7 + CH2O { A = 7.25E+39 n = -7.59 E = 140.03 }
1971 #C35 : T-C4H9O -> CH3COCH3 + CH3 { A = 3.09E+13 n = 0.03 E = 58.87 }
1972
1973 # Reactions of T-C4H8
1974 # (not lumped)
1975
1976 IC36 : T-C4H8 -> T-C3H5 + CH3 { A = 1.92E+66 n =-14.22 E = 535.97 }
1977 IC37 : T-C4H8 + H -> C3H6 + CH3 { A = 5.68E+33 n = -5.72 E = 83.68 }
1978
1979 IC38 : T-C4H8 + H -> T-C4H7 + H2 { A = 3.40E+05 n = 2.50 E = 10.43 }
1980 IC39 : T-C4H8 + O -> T-C4H7 + OH { A = 1.21E+11 n = 0.70 E = 31.94 }
1981 IC40 : T-C4H8 + OH -> T-C4H7 + H2O { A = 5.20E+06 n = 2.00 E = -1.25 }
1982 IC41 : T-C4H8 + CH3 -> T-C4H7 + CH4 { A = 4.42E+00 n = 3.50 E = 23.74 }
1983 IC42 : T-C4H8 + HO2 -> T-C4H7 + H2O2 { A = 1.93E+04 n = 2.60 E = 58.20 }
1984
1985 #C43 : T-C4H8 + O -> I-C3H7 + HCO { A = 1.58E+07 n = 1.76 E = -5.09 }
1986 #C44 : T-C4H8 + O -> CH2CO + 2 CH3 { A = 3.33E+07 n = 1.76 E = 0.32 }
1987
1988 # Reactions of T-C4H7
1989 # (not lumped)
1990
1991 IC45 : T-C4H7 -> A-C3H4 + CH3 { A = 1.23E+47 n = -9.74 E = 310.70 }
1992
1993 #C46 : T-C4H7 + O -> I-C3H5CHO + H { A = 6.03E+13 n = .00 E = .00 }
1994 #C47 : T-C4H7 + O2 -> I-C3H5CHO + OH { A = 2.47E+13 n = -0.45 E = 96.32 }
1995 #C48 : T-C4H7 + O2 -> CH2CO + CH2O + CH3 { A = 7.14E+15 n = -1.21 E = 88.07 }
1996 #C49 : T-C4H7 + O2 -> A-C3H4 + CH2O + OH { A = 7.29E+29 n = -5.71 E = 89.75 }
1997 #C50 : T-C4H7 + HO2 -> T-C4H7O + OH { A = 7.00E+12 n = .00 E = -4.18 }
1998
1999 # Reactions of T-C4H7O
2000 # (not lumped)
2001
2002 #C51 : T-C4H7O -> I-C3H5CHO + H { A = 5.00E+13 n = .00 E = 121.75 }
2003 #C52 : T-C4H7O -> T-C3H5 + CH2O { A = 2.93E+21 n = -2.39 E = 148.91 }
2004 #C53 : T-C4H7O + O2 -> I-C3H5CHO + HO2 { A = 3.00E+10 n = .00 E = 6.90 }
2005
2006 # Reactions of I-C3H5CHO
2007 # (not lumped)
2008
2009 #C54 : I-C3H5CHO -> T-C3H5 + HCO { A = 3.05E+23 n = -2.37 E = 415.22 }
2010
2011 #C55 : I-C3H5CHO + H -> T-C3H5 + CO + H2 { A = 2.60E+12 n = .00 E = 10.88 }
2012 #C56 : I-C3H5CHO + O -> T-C3H5 + CO + OH { A = 7.18E+12 n = .00 E = 5.81 }
2013 #C57 : I-C3H5CHO + OH -> T-C3H5 + CO + H2O { A = 2.69E+10 n = 0.76 E = -1.42 }
2014 #C58 : I-C3H5CHO + CH3 -> T-C3H5 + CO + CH4 { A = 3.98E+12 n = .00 E = 36.40 }
2015 #C59 : I-C3H5CHO + HO2 -> T-C3H5 + CO + H2O2 { A = 1.00E+12 n = .00 E = 49.87 }
2016
2017 # Reactions of CH3COCH3
2018 # Revised from LLNL-NC16
2019 # (not lumped)
2020
2021 IC60 : CH3COCH3 -> 2 CH3 + CO { A = 1.22E+23 n = -1.99 E = 351.25 }
2022
2023 IC61 : CH3COCH3 + H -> CH2CO + CH3 + H2 { A = 2.30E+05 n = 2.72 E = 26.19 }
2024 IC62 : CH3COCH3 + O -> CH2CO + CH3 + OH { A = 5.13E+11 n = 0.21 E = 20.46 }
2025 IC63 : CH3COCH3 + OH -> CH2CO + CH3 + H2O { A = 3.38E+07 n = 1.74 E = 3.47 }
2026 IC64 : CH3COCH3 + O2 -> CH2CO + CH3 + HO2 { A = 6.03E+13 n = .00 E = 202.92 }
2027 IC65 : CH3COCH3 + CH3 -> CH2CO + CH3 + CH4 { A = 3.96E+11 n = .00 E = 40.94 }
2028 IC66 : CH3COCH3 + HO2 -> CH2CO + CH3 + H2O2 { A = 1.70E+13 n = .00 E = 85.61 }
2029
2030
2031
2032 #==========================================================================#
2033 # #
2034 # Zhong & Bozzelli, Int. J. Chem. Kinet., 1997, 29, 893-913 #
2035 # Zhong & Bozzelli, J. Phys. Chem. A, 1998, 102, 3537-3555 #
2036 # Robinson & Lindstedt, Comb. Flame, 2011, 158, 666-686 #
2037 # #
2038 #==========================================================================#
2039
2040
2041 # Cyclopentadiene
2042 # ---------------
2043
2044 # Robinson & Lindstedt 2011
2045 CP01f: C5H6 -> C5H5 + H { A = 3.24E+49 n =-10.01 E = 423.40 }
2046 CP02f: C5H6 + H -> C5H5 + H2 { A = 8.59E+07 n = 1.85 E = 13.97 }
2047
2048 CP03f: C5H6 + H -> A-C3H5 + C2H2 { A = 7.74E+36 n = -6.81 E = 137.60 }
2049
2050 CP04f: C5H6 + O -> C5H5 + OH { A = 4.77E+04 n = 2.71 E = 4.63 }
2051 CP05f: C5H6 + OH -> C5H5 + H2O { A = 3.08E+06 n = 2.00 E = .00 }
2052 CP06f: C5H6 + O2 -> C5H5 + HO2 { A = 1.00E+14 n = .00 E = 155.44 }
2053 CP07f: C5H6 + HO2 -> C5H5 + H2O2 { A = 1.10E+04 n = 2.60 E = 53.97 }
2054 CP08f: C5H6 + CH3 -> C5H5 + CH4 { A = 1.80E-01 n = 4.00 E = .00 }
2055
2056 # From CH4 + ?? (x0.5)
2057 CP09f: C5H6 + C2H3 -> C5H5 + C2H4 { A = 5.55E+04 n = 2.02 E = 13.17 }
2058 CP10f: C5H6 + A-C3H5 -> C5H5 + C3H6 { A = 2.15E+01 n = 3.31 E = 106.79 }
2059 CP11f: C5H6 + N-C4H5 -> C5H5 + C4H6 { A = 7.30E+10 n = 0.76 E = 63.51 }
2060
2061
2062 # Cyclopentadienyl radical
2063 # ------------------------
2064
2065 # Moskaleva & Lin 2000
2066 # Knyazev & Slagle 2002
2067 CP16f: C3H3 + C2H2 -> C5H5 { A = 6.87E+55 n =-12.50 E = 175.80 }
2068
2069 # Melius, Colvin, Marinov, Pitz, & Senkan 1996
2070 # Sharma & Green 2009 - Rate fitted at P=1bar
2071 # PRODUCTS TO BE CHECKED - Should be benzene?
2072 CP17 : C5H5 + CH3 -> C5H4CH2 + 2H { A = 4.91E+31 n = -4.85 E = 103.65 }
2073
2074 # Murakami et al. 2003 - Total rate
2075 # Kislov & Mebel - Branching ratio
2076 CP18 : C5H5 + C5H5 -> A2-C10H8 + 2H { A = 6.39E+29 n = -4.03 E = 147.30 }
2077
2078 # Robinson & Lindstedt 2011
2079 # estimated
2080 CP19f: C5H5 + C5H5 -> C9H7 + CH3 { A = 2.50E+12 n = .00 E = 40.00 }
2081
2082 # Kislov & Mebel 2008 - Full entrance rate
2083 CP20 : C5H5 + C5H6 -> C9H8 + CH3 { A = 7.86E-01 n = 3.07 E = 23.97 }
2084
2085 # Robinson & Lindstedt 2011
2086 CP21f: C5H5 + O -> N-C4H5 + CO { A = 1.27E+14 n = 0.26 E = 16.50 }
2087 CP22f: C5H5 + OH -> C4H6 + CO { A = 8.53E+13 n = 0.25 E = 18.20 }
2088 CP23f: C5H5 + OH -> C5H5O + H { A = 1.11E+05 n = 1.90 E = 138.60 }
2089 CP24f: C5H5 + O2 -> C5H4O + OH { A = 9.11E+15 n = -2.21 E = 10.20 }
2090 CP25f: C5H5 + O2 -> C5H5O + O { A = 4.37E+03 n = 2.40 E = 211.50 }
2091 CP26f: C5H5 + HO2 -> C5H5O + OH { A = 6.86E+13 n = 0.25 E = 21.30 }
2092
2093
2094 # Cyclopentadienoxy radical
2095 # -------------------------
2096
2097 # Robinson & Lindstedt 2011
2098 CP27 : C5H5O -> C5H4O + H { A = 8.18E+16 n = -2.32 E = 36.50 }
2099 CP28 : C5H5O -> N-C4H5 + CO { A = 2.15E+64 n =-15.14 E = 278.00 }
2100
2101 # 1/3 rate from CH3O
2102 CP29f: C5H5O + H -> C5H4O + H2 { A = 6.67E+12 n = .00 E = .00 }
2103 CP30f: C5H5O + O -> C5H4O + OH { A = 3.33E+12 n = .00 E = .00 }
2104 CP31f: C5H5O + OH -> C5H4O + H2O { A = 1.67E+12 n = .00 E = .00 }
2105 CP32f: C5H5O + O2 -> C5H4O + HO2 { A = 7.22E+09 n = .00 E = 7.32 }
2106
2107
2108 # Cyclopentadienone
2109 # -----------------
2110
2111 # Wang & Brezinsky 1998
2112 # Ristori et al. 2001
2113 # (products guessed)
2114 CP33 : C5H4O -> 2 C2H2 + CO { A = 6.20E+41 n = -7.87 E = 413.00 }
2115 CP34 : C5H4O -> C4H4 + CO { A = 5.00E+11 n = .00 E = 221.80 }
2116
2117 # From C2H4+R, C3H6+H
2118 # (products guessed)
2119 CP35 : C5H4O + H -> C2H3 + C2H2 + CO { A = 2.67E+12 n = 0.47 E = 22.72 }
2120 CP36 : C5H4O + O -> C3H3 + HCO + CO { A = 1.02E+08 n = 1.66 E = 2.75 }
2121
2122
2123
2124 #==========================================================================#
2125 # #
2126 # "Detailed kinetic modeling of benzene and toluene oxidation #
2127 # at high temperatures" #
2128 # Zoran M. Djurisic - Master's Thesis #
2129 # http://diesel.me.berkeley.edu/~zoran/publications/2000_MS_Thesis/ #
2130 # #
2131 #==========================================================================#
2132
2133
2134 # Benzene
2135 # -------
2136
2137 # Miller & Klippenstein 2003 (1bar)
2138 # Updated to include HPL from Harding et al. 2005
2139 BN00f: A1-C6H6 -> A1--C6H5 + H { A = 1.29E+61 n =-12.48 E = 619.59 }
2140
2141 # Mebel & Lin 1997
2142 BN01f: A1-C6H6 + H -> A1--C6H5 + H2 { A = 6.02E+08 n = 1.80 E = 68.42 }
2143
2144 # Lindsted & Skevis 1994
2145 BN02f: A1-C6H6 + O -> A1--C6H5 + OH { A = 2.00E+13 n = .00 E = 61.50 }
2146
2147 # Seta, Nakajima & Miyoshi 2006
2148 BN03f: A1-C6H6 + OH -> A1--C6H5 + H2O { A = 2.34E+04 n = 2.68 E = 3.07 }
2149 BN04f: A1-C6H6 + OH -> A1OH-C6H6O + H { A = 1.32E+02 n = 3.25 E = 23.39 }
2150
2151 # From C2H4 + O2 (x1.5)
2152 # Hua, Ruscic, Wang 2005
2153 # Backward ~ 2e12
2154 BN05f: A1-C6H6 + O2 -> A1--C6H5 + HO2 { A = 4.34E+14 n = .00 E = 269.00 }
2155
2156 # Taatjes, Wang, et al. 2010
2157 # Refitted
2158 BN06f: A1-C6H6 + O -> A1O-C6H5O + H { A = 1.99E+07 n = 1.80 E = 16.63 }
2159 BN07f: A1-C6H6 + O -> A1OH-C6H6O { A = 1.53E+10 n = 0.92 E = 13.79 }
2160 BN08f: A1-C6H6 + O -> C5H6 + CO { A = 1.53E+17 n = -0.89 E = 64.89 }
2161
2162
2163 # Phenyl radical
2164 # --------------
2165
2166 # Wang et al. 2000
2167 BN09f: A1--C6H5 + M9 -> O-C6H4 + H + M9 { A = 1.00E+84 n =-18.87 E = 376.98
2168 Ai= 4.30E+12 ni= 0.62 Ei= 323.43
2169 fcA = 0.098 fctA = 696
2170 fcb = 0.902 fctb = 358
2171 fcc = 1.0 fctc = 3856 }
2172
2173 # da Silva, Chen & Bozzelli 2007
2174 # From 3/4-methylphenyl + O2
2175 BN10f: A1--C6H5 + O2 -> A1O-C6H5O + O { A = 8.57E+20 n = -2.27 E = 30.08 }
2176
2177 # Frank, Herzler, Just & Wahl 1994
2178 BN11f: A1--C6H5 + O2 -> OC6H4O + H { A = 3.00E+13 n = .00 E = 37.58 }
2179 BN12f: A1--C6H5 + O -> A1O-C6H5O { A = 1.00E+14 n = .00 E = .00 }
2180
2181 BN13f: A1--C6H5 + OH -> A1O-C6H5O + H { A = 3.00E+13 n = .00 E = .00 }
2182 BN14f: A1--C6H5 + HO2 -> A1O-C6H5O + OH { A = 3.00E+13 n = .00 E = .00 }
2183
2184 # Tokmakov & Lin 1999/2002
2185 BN15f: A1--C6H5 + CH4 -> A1-C6H6 + CH3 { A = 3.89E-03 n = 4.57 E = 22.00 }
2186
2187
2188 # Phenol
2189 # ------
2190
2191 # Xu & Lin 2006
2192 # Rates for 1 atm
2193 # Formation of CO x0.765 to better match Horn & Roy 1989
2194 BN16f: A1OH-C6H6O -> C5H6 + CO { A = 6.59E+15 n = -0.61 E = 310.11 }
2195 BN17f: A1OH-C6H6O -> A1O-C6H5O + H { A = 1.01E+71 n =-15.92 E = 522.12 }
2196
2197 # From CH3OH+R
2198 BN18f: A1OH-C6H6O + H -> A1O-C6H5O + H2 { A = 4.20E+06 n = 2.10 E = 20.38 }
2199 BN19f: A1OH-C6H6O + OH -> A1O-C6H5O + H2O { A = 6.30E+06 n = 2.00 E = 6.28 }
2200 BN20f: A1OH-C6H6O + CH3 -> A1O-C6H5O + CH4 { A = 1.00E+07 n = 1.50 E = 41.59 }
2201
2202 # Brezinsky et al. 1998
2203 #N21f: A1OH-C6H6O + O2 -> A1O-C6H5O + HO2 { A = 7.32E+13 n = .00 E = 173.22 }
2204
2205
2206 # Phenoxy radical
2207 # 2-B1 state for O=C6H5
2208 # ---------------------
2209
2210 # Murakami et al. 2003
2211 BN22f: A1O-C6H5O -> C5H5 + CO { A = 2.90E+10 n = .00 E = 152.40 }
2212
2213 # From C2H5 + O (x2)
2214 BN23f: A1O-C6H5O + O -> OC6H4O + H { A = 6.34E+13 n = 0.03 E = -1.65 }
2215
2216 # From A-C3H5 + O2 - Total rate (x3/2)
2217 BN24f: A1O-C6H5O + O2 -> OC6H4O + OH { A = 6.51E+07 n = 1.30 E = 73.92 }
2218
2219
2220 # p-Benzoquinone
2221 # Thermoprop & Reactions for para
2222 # -------------------------------
2223
2224 BN25 : OC6H4O -> C5H4O + CO { A = 7.40E+11 n = .00 E = 246.86 }
2225
2226 BN26 : OC6H4O + H -> C5H5O + CO { A = 4.30E+09 n = 1.45 E = 16.18 }
2227 BN27 : OC6H4O + O -> CH2CO + C2H2 + 2 CO { A = 3.00E+13 n = .00 E = 20.92 }
2228
2229
2230 # Benzyne
2231 # -------
2232
2233 # Wang, Laskin, Moriarty, Frenklach 2000
2234 BN28 : O-C6H4 -> C4H2 + C2H2 { A = 1.20E+18 n = -0.34 E = 367.48 }
2235
2236 # Wang & Frenklach 1997
2237 BN29f: N-C4H3 + C2H2 -> O-C6H4 + H { A = 6.90E+46 n =-10.01 E = 125.94 }
2238
2239 BN30 : O-C6H4 + OH -> C5H5 + CO { A = 1.00E+13 n = .00 E = .00 }
2240
2241
2242
2243 #==========================================================================#
2244 # #
2245 # Toluene chemistry #
2246 # #
2247 # Oehlschlaeger, Davidson & Hanson, Comb. Flame, 2006, 147, 195-208 #
2248 # #
2249 #==========================================================================#
2250
2251
2252 # Toluene / Benzyl decomposition
2253 # ------------------------------
2254
2255 # Tokmakov et al. 2001 (x1.2 to match exp.)
2256 # Sheen, Rosado-Reyes, Tsang 2013 (within 2%)
2257 T01f: A1CH3-C7H8 + H -> A1-C6H6 + CH3 { A = 2.31E+06 n = 2.17 E = 17.42 }
2258
2259 # Klippenstein et al. 2007
2260 # Almost indep or pressure => HPL
2261 T02f: A1CH3-C7H8 -> A1CH2-C7H7 + H { A = 1.56E+13 n = 0.68 E = 373.24 }
2262 T03f: A1CH3-C7H8 -> A1--C6H5 + CH3 { A = 4.35E+22 n = -1.73 E = 436.01 }
2263 # P=1bar - 1000K-2500K
2264 T04f: A1CH2-C7H7 + H -> A1--C6H5 + CH3 { A = 5.83E+67 n =-14.15 E = 285.89 }
2265
2266 # Assumed products. Other choices: C7H6 + H, c-C7H7
2267 # Rate from Oehlschlaeger et al. 2006 (1.5 atm)
2268 T05f: A1CH2-C7H7 -> C5H5 + C2H2 { A = 8.20E+14 n = .00 E = 337.55 }
2269
2270
2271 # Toluene
2272 # -------
2273
2274 # Oehlschlaeger et al. 2006 (1.5 atm)
2275 T06f: A1CH3-C7H8 + H -> A1CH2-C7H7 + H2 { A = 6.47E+00 n = 3.98 E = 14.16 }
2276
2277 # From C3H8+O (x0.5)
2278 T07f: A1CH3-C7H8 + O -> A1CH2-C7H7 + OH { A = 9.50E+04 n = 2.68 E = 15.55 }
2279
2280 # From A1+O (x5/6)
2281 T08f: A1CH3-C7H8 + O -> OA1CH3-C7H7O + H { A = 1.66E+07 n = 1.80 E = 16.63 }
2282 T09f: A1CH3-C7H8 + O -> HOA1CH3-C7H8O { A = 1.28E+10 n = 0.92 E = 13.79 }
2283
2284 # Seta, Nakajima & Miyoshi 2006
2285 # Better match with Vasudevan, Davidson & Hanson 2005
2286 T10f: A1CH3-C7H8 + OH -> A1CH2-C7H7 + H2O { A = 1.77E+05 n = 2.39 E = -2.52 }
2287 T11f: A1CH3-C7H8 + OH -> A1OH-C6H6O + CH3 { A = 7.83E+02 n = 2.88 E = 13.48 }
2288 T12f: A1CH3-C7H8 + OH -> HOA1CH3-C7H8O + H { A = 3.14E+01 n = 3.37 E = 19.75 }
2289
2290 # Oehlschlaeger et al. 2006 (1.5 atm)
2291 T13f: A1CH3-C7H8 + O2 -> A1CH2-C7H7 + HO2 { A = 2.18E+07 n = 2.50 E = 192.65 }
2292
2293 # Baulch et al. 2005
2294 T14f: A1CH3-C7H8 + HO2 -> A1CH2-C7H7 + H2O2 { A = 9.33E+04 n = 2.50 E = 61.44 }
2295
2296 # From C3H8+CH3 (x0.5)
2297 T15f: A1CH3-C7H8 + CH3 -> A1CH2-C7H7 + CH4 { A = 4.52E-01 n = 3.65 E = 29.93 }
2298
2299 # Heckmann, Hippler & Troe 1996
2300 T16f: A1CH3-C7H8 + A1--C6H5 -> A1CH2-C7H7 + A1-C6H6 { A = 7.94E+13 n = .00 E = 50.00 }
2301
2302
2303 # Benzyl radical
2304 # --------------
2305
2306 # da Silva & Bozzelli 2012 - P=1atm
2307 T17f: A1CH2-C7H7 + O -> A1-C6H6 + HCO { A = 6.98E+12 n = 0.33 E = 2.87 }
2308 T18f: A1CH2-C7H7 + O -> A1CHO-C7H6O + H { A = 2.75E+13 n = 0.07 E = 3.06 }
2309
2310 # Murakami et al. 2007 - HPL
2311 # Canneaux et al. 2008 - Benzylperoxy isomerization
2312 # Benzylperoxy in Steady State
2313 T19f: A1CH2-C7H7 + O2 -> A1CHO-C7H6O + OH { A = 3.76E+15 n = -1.55 E = 47.37 }
2314
2315 # da Silva & Bozzelli 2008
2316 T21f: A1CH2-C7H7 + HO2 -> A1CH2O-C7H7O + OH { A = 1.19E+09 n = 1.03 E = -9.41 }
2317
2318 # From A-C3H5
2319 T22 : A1CH2-C7H7 + C3H3 -> A2-C10H8 + 2H { A = 1.88E+38 n = -7.53 E = 99.91 }
2320
2321
2322 # Alcoxy Benzyl
2323 # -------------
2324
2325 # Choi, Xia, Park & Lin 2000
2326 T23f: A1--C6H5 + CH2O -> A1-C6H6 + HCO { A = 8.55E+04 n = 2.19 E = 0.16 }
2327
2328 # Xia & Lin 2000
2329 T24f: A1CH2O-C7H7O -> A1CHO-C7H6O + H { A = 1.27E+13 n = .00 E = 86.19 }
2330
2331 # da Silva & Bozzelli 2009 - P=1atm
2332 T25f: A1CH2O-C7H7O -> A1--C6H5 + CH2O { A = 7.21E+33 n = -6.21 E = 154.18 }
2333 T26f: A1CH2O-C7H7O -> A1-C6H6 + HCO { A = 2.37E+32 n = -6.10 E = 120.54 }
2334
2335 # From CH3O (x2/3)
2336 T27f: A1CH2O-C7H7O + H -> A1CHO-C7H6O + H2 { A = 1.33E+13 n = .00 E = .00 }
2337 T28f: A1CH2O-C7H7O + O -> A1CHO-C7H6O + OH { A = 6.67E+12 n = .00 E = .00 }
2338 T29f: A1CH2O-C7H7O + OH -> A1CHO-C7H6O + H2O { A = 3.33E+12 n = .00 E = .00 }
2339 T30f: A1CH2O-C7H7O + O2 -> A1CHO-C7H6O + HO2 { A = 4.11E+10 n = .00 E = 7.32 }
2340
2341
2342 # Benzaldehyde
2343 # ------------
2344
2345 # From CH3CHO
2346 # Grela & Colussi 1986 - Loss of H then loss of CO
2347 T31 : A1CHO-C7H6O -> A1--C6H5 + CO + H { A = 2.72E+22 n = -1.74 E = 361.33 }
2348
2349 # From CH3CHO
2350 T32 : A1CHO-C7H6O + H -> A1--C6H5 + CO + H2 { A = 1.31E+05 n = 2.58 E = 5.10 }
2351 T33 : A1CHO-C7H6O + O -> A1--C6H5 + CO + OH { A = 1.95E+13 n = .00 E = 14.81 }
2352 T34 : A1CHO-C7H6O + OH -> A1--C6H5 + CO + H2O { A = 9.70E+05 n = 2.11 E = -7.06 }
2353 T35 : A1CHO-C7H6O + CH3 -> A1--C6H5 + CO + CH4 { A = 1.55E+00 n = 3.70 E = 19.10 }
2354
2355
2356 # Cresol
2357 # All isomers lumped into meta
2358 # ----------------------------
2359
2360 # From A1OH/A1O
2361 T36f: HOA1CH3-C7H8O -> OA1CH3-C7H7O + H { A = 1.01E+71 n =-15.92 E = 522.12 }
2362 T37f: HOA1CH3-C7H8O + H -> OA1CH3-C7H7O + H2 { A = 4.20E+06 n = 2.10 E = 20.38 }
2363 T38f: HOA1CH3-C7H8O + O -> OA1CH3-C7H7O + OH { A = 1.30E+05 n = 2.50 E = 20.92 }
2364 T39f: HOA1CH3-C7H8O + OH -> OA1CH3-C7H7O + H2O { A = 6.30E+06 n = 2.00 E = 6.28 }
2365 T40f: HOA1CH3-C7H8O + CH3-> OA1CH3-C7H7O + CH4 { A = 1.00E+07 n = 1.50 E = 41.59 }
2366
2367 T41 : OA1CH3-C7H7O -> C5H4CH2 + CO + H { A = 2.90E+10 n = .00 E = 152.40 }
2368
2369
2370 # Methyl-phenyl
2371 # All isomers lumped into meta
2372 # ----------------------------
2373
2374 # From A1 (x0.65)
2375 # From symmetry should be x5/6
2376 # Seta, Nakajima & Miyoshi 2006 - Rate for OH - Same as A1 x0.65
2377 T42f: A1CH3-C7H8 -> A1CH3*-C7H7 + H { A = 8.39E+60 n =-12.48 E = 619.59 }
2378 T43f: A1CH3-C7H8 + H -> A1CH3*-C7H7 + H2 { A = 3.91E+08 n = 1.80 E = 68.42 }
2379 T44f: A1CH3-C7H8 + O -> A1CH3*-C7H7 + OH { A = 1.60E+13 n = .00 E = 61.50 }
2380 T45f: A1CH3-C7H8 + OH -> A1CH3*-C7H7 + H2O { A = 1.36E+04 n = 2.69 E = 2.59 }
2381 T46f: A1CH3-C7H8 + CH3 -> A1CH3*-C7H7 + CH4 { A = 1.79E-02 n = 4.46 E = 57.06 }
2382
2383 # From A1-
2384 T47f: A1CH3*-C7H7 + O -> OA1CH3-C7H7O { A = 1.00E+14 n = .00 E = .00 }
2385 T48f: A1CH3*-C7H7 + OH -> OA1CH3-C7H7O + H { A = 3.00E+13 n = .00 E = .00 }
2386 T49f: A1CH3*-C7H7 + HO2 -> OA1CH3-C7H7O + OH { A = 3.00E+13 n = .00 E = .00 }
2387
2388 # da Silva, Chen & Bozzelli 2007
2389 # Assumed products for methyloxepinoxy decomposition
2390 T50f: A1CH3*-C7H7 + O2 -> OA1CH3-C7H7O + O { A = 8.57E+20 n = -2.27 E = 30.08 }
2391 T51 : A1CH3*-C7H7 + O2 -> C5H4CH2 + CO2 + H { A = 2.55E+13 n = -0.44 E = -6.90 }
2392 T52 : A1CH3*-C7H7 + O2 -> P-C3H4 + C2H3 + 2CO { A = 2.55E+13 n = -0.44 E = -6.90 }
2393
2394
2395
2396 #===============================================================================#
2397 # #
2398 # Styrene Chemistry #
2399 # Adapted from C2H4 chemistry #
2400 # Additional rates from Kislov & Mebel 2005 #
2401 # #
2402 #===============================================================================#
2403
2404
2405 # Styrene
2406 # -------
2407
2408 # Greda et al. 1992
2409 ST01 : A1C2H3-C8H8 -> A1-C6H6 + H2C2 { A = 2.40E+14 n = .00 E = 326.90 }
2410
2411 # Wang & Frenklach 1997 - estimated HPL
2412 ST02f: A1--C6H5 + C2H3 -> A1C2H3-C8H8 { A = 6.00E+12 n = .00 E = .00 }
2413
2414 # Tokmakov & Lin 2004
2415 ST03f: A1--C6H5 + C2H4 -> A1C2H3-C8H8 + H { A = 3.62E+28 n = -4.24 E = 99.85 }
2416 ST04f: A1C2H3-C8H8 + H -> A1-C6H6 + C2H3 { A = 5.62E+24 n = -3.00 E = 82.97 }
2417
2418 # From A1CH3
2419 ST05f: A1C2H3-C8H8 + OH -> A1OH-C6H6O + C2H3 { A = 7.83E+02 n = 2.88 E = 13.48 }
2420
2421 # From C2H4 (x0.5)
2422 ST06f: A1C2H3-C8H8 -> A1C2H2-C8H7 + H { A = 3.01E+14 n = 0.34 E = 465.49 }
2423 ST07f: A1C2H3-C8H8 + H -> A1C2H2-C8H7 + H2 { A = 6.35E+04 n = 2.75 E = 48.74 }
2424 ST08f: A1C2H3-C8H8 + OH -> A1C2H2-C8H7 + H2O { A = 1.12E+04 n = 2.75 E = 9.27 }
2425
2426 # From A1 (x1/3)
2427 ST09f: A1C2H3-C8H8 -> A1C2H3*-C8H7 + H { A = 4.30E+60 n =-12.48 E = 619.59 }
2428 ST10f: A1C2H3-C8H8 + H -> A1C2H3*-C8H7 + H2 { A = 2.01E+08 n = 1.80 E = 68.42 }
2429 ST11f: A1C2H3-C8H8 + OH -> A1C2H3*-C8H7 + H2O { A = 7.80E+03 n = 2.68 E = 3.07 }
2430
2431 # From C2H4 (x0.5)
2432 # Half for each carbon atoms
2433 ST12f: A1C2H3-C8H8 + O -> A1CH2-C7H7 + HCO { A = 1.95E+08 n = 1.36 E = 3.71 }
2434 ST13f: A1C2H3-C8H8 + O -> A1CHO-C7H6O + T-CH2 { A = 3.58E+04 n = 2.47 E = 3.89 }
2435
2436
2437 # Styryl radical
2438 # --------------
2439
2440 # Tolkmakov & Lin 2003
2441 ST16f: A1--C6H5 + C2H2 -> A1C2H-C8H6 + H { A = 2.66E+32 n = -5.30 E = 99.52 }
2442 ST17f: A1--C6H5 + C2H2 -> A1C2H2-C8H7 { A = 4.80E+44 n = -9.90 E = 73.75 }
2443
2444 # Kislov & Mebel 2005 - HPL
2445 ST18f: A1C2H2-C8H7 -> A1C2H3*-C8H7 { A = 5.90E+10 n = 0.55 E = 115.34 }
2446
2447 # From N-C4H5
2448 ST19f: A1C2H2-C8H7 -> A1C2H-C8H6 + H { A = 1.81E+54 n =-12.69 E = 215.02 }
2449 ST20f: A1C2H2-C8H7 + H -> A1C2H-C8H6 + H2 { A = 1.50E+13 n = .00 E = .00 }
2450 ST21f: A1C2H2-C8H7 + OH -> A1C2H-C8H6 + H2O { A = 2.50E+12 n = .00 E = .00 }
2451 ST22f: A1C2H2-C8H7 + O2 -> A1C2H-C8H6 + HO2 { A = 6.70E+05 n = 1.61 E = -1.61 }
2452
2453 # From C2H3 + O
2454 ST23f: A1C2H2-C8H7 + O -> A1CH2-C7H7 + CO { A = 1.03E+13 n = 0.21 E = -1.79 }
2455
2456 # From C2H3 + O2
2457 ST24 : A1C2H2-C8H7 + O2 -> A1CH2-C7H7 + CO + O { A = 3.80E+11 n = 0.19 E = 0.20 }
2458 ST25f: A1C2H2-C8H7 + O2 -> A1CHO-C7H6O + HCO { A = 4.05E+17 n = -1.86 E = 4.88 }
2459 ST26 : A1C2H2-C8H7 + O2 -> A1CHO-C7H6O + CO + H { A = 2.22E+16 n = -1.35 E = 3.28 }
2460
2461
2462 # Ethynylbenzene
2463 # --------------
2464
2465 # Goulay & Leone 2006
2466 # Woon, Park & Jin-Young 2009
2467 ST27f: A1-C6H6 + C2H -> A1C2H-C8H6 + H { A = 2.00E+14 n = .00 E = .00 }
2468
2469 # From A1 (x1/3)
2470 ST28f: A1C2H-C8H6 -> A1C2H*-C8H5 + H { A = 4.30E+60 n =-12.48 E = 619.59 }
2471 ST29f: A1C2H-C8H6 + H -> A1C2H*-C8H5 + H2 { A = 2.01E+08 n = 1.80 E = 68.42 }
2472 ST30f: A1C2H-C8H6 + OH -> A1C2H*-C8H5 + H2O { A = 7.80E+03 n = 2.68 E = 3.07 }
2473
2474 # From C2H2
2475 ST31f: A1C2H-C8H6 + O -> A1--C6H5 + HCCO { A = 3.70E+09 n = 1.28 E = 10.34 }
2476
2477 ST32f: A1C2H-C8H6 + OH -> A1--C6H5 + CH2CO { A = 2.10E+01 n = 3.22 E = -1.76 }
2478 ST33f: A1C2H-C8H6 + OH -> A1CH2-C7H7 + CO { A = 6.40E+08 n = 0.73 E = 10.79 }
2479
2480
2481
2482 #==========================================================================#
2483 # #
2484 # Ethyl-Benzene chemistry #
2485 # #
2486 # Adapted from C3H8 and Toluene/Benzene chemistry #
2487 # #
2488 #==========================================================================#
2489
2490
2491 # Ethylbenzene
2492 # ------------
2493
2494 # Estimated from C3H7+H - HPL
2495 EB01f: A1C2H4-C8H9 + H -> A1C2H5-C8H10 { A = 3.61E+13 n = .00 E = .00 }
2496
2497 # Estimated from C2H5+CH3 - HPL
2498 EB02f: A1CH2-C7H7 + CH3 -> A1C2H5-C8H10 { A = 2.00E+13 n = .00 E = .00 }
2499 EB03f: A1--C6H5 + C2H5 -> A1C2H5-C8H10 { A = 2.00E+13 n = .00 E = .00 }
2500
2501 # From A1CH3
2502 EB04f: A1C2H5-C8H10 + H -> A1-C6H6 + C2H5 { A = 2.31E+06 n = 2.17 E = 17.42 }
2503 EB05f: A1C2H5-C8H10 + OH -> A1OH-C6H6O + C2H5 { A = 7.83E+02 n = 2.88 E = 13.48 }
2504
2505 # From C3H8 (x0.5)
2506 EB06f: A1C2H5-C8H10 + H -> A1C2H4-C8H9 + H2 { A = 4.68E+07 n = 1.97 E = 34.31 }
2507 EB07f: A1C2H5-C8H10 + O -> A1C2H4-C8H9 + OH { A = 9.95E+04 n = 2.68 E = 15.55 }
2508 EB08f: A1C2H5-C8H10 + OH -> A1C2H4-C8H9 + H2O { A = 2.67E+03 n = 2.94 E = -1.75 }
2509 EB09f: A1C2H5-C8H10 + CH3 -> A1C2H4-C8H9 + CH4 { A = 4.52E-01 n = 3.65 E = 29.93 }
2510 EB10f: A1C2H5-C8H10 + HO2 -> A1C2H4-C8H9 + H2O2 { A = 2.38E+04 n = 2.55 E = 69.00 }
2511
2512
2513 # N-Ethylbenzene radical
2514 # ----------------------
2515
2516 # Tokmakov & Lin 2004
2517 # HPL for both decompositions
2518 EB11f: A1C2H4-C8H9 -> A1--C6H5 + C2H4 { A = 1.72E+11 n = 0.78 E = 161.94 }
2519 EB12f: A1C2H4-C8H9 -> A1C2H3-C8H8 + H { A = 3.79E+06 n = 1.99 E = 134.33 }
2520
2521 # From N-C3H7
2522 EB13f: A1C2H4-C8H9 + O -> A1CH2-C7H7 + CH2O { A = 9.60E+13 n = .00 E = .00 }
2523
2524 # From N-C3H7
2525 EB14f: A1C2H4-C8H9 + H -> A1C2H3-C8H8 + H2 { A = 1.80E+12 n = .00 E = .00 }
2526 EB15f: A1C2H4-C8H9 + OH -> A1C2H3-C8H8 + H2O { A = 2.41E+13 n = .00 E = .00 }
2527 EB16f: A1C2H4-C8H9 + CH3 -> A1C2H3-C8H8 + CH4 { A = 3.31E+12 n = .00 E = -3.22 }
2528
2529 # Altarawneh, Dlugogorski, Kennedy, Mackie 2013
2530 EB17f: A1C2H4-C8H9 + O2 -> A1C2H3-C8H8 + HO2 { A = 3.08E+13 n = .00 E = 75.66 }
2531
2532 # From NC7
2533 EB18 : A1C2H4-C8H9 + HO2 -> A1CH2-C7H7 + CH2O + OH{ A = 7.00E+12 n = .00 E = -4.18 }
2534
2535
2536 #=========================================================================#
2537 # #
2538 # Xylene Oxidation Chemistry #
2539 # Adapted from Toluene Chemistry #
2540 # #
2541 #=========================================================================#
2542
2543
2544 # Xylene
2545 # ------
2546
2547 # From A1CH3 (x2)
2548 XY01f: A1CH3CH3-C8H10 -> A1CH3CH2-C8H9 + H { A = 2.12E+13 n = 0.68 E = 373.24 }
2549 XY02f: A1CH3CH3-C8H10 -> A1CH3*-C7H7 + CH3 { A = 8.70E+22 n = -1.73 E = 436.01 }
2550
2551 # From A1CH3+R (x2)
2552 XY03f: A1CH3CH3-C8H10 + H -> A1CH3CH2-C8H9 + H2 { A = 1.29E+01 n = 3.98 E = 14.16 }
2553 XY04f: A1CH3CH3-C8H10 + O -> A1CH3CH2-C8H9 + OH { A = 1.90E+05 n = 2.68 E = 15.55 }
2554 XY05f: A1CH3CH3-C8H10 + OH -> A1CH3CH2-C8H9 + H2O { A = 3.54E+05 n = 2.39 E = -2.52 }
2555 XY06f: A1CH3CH3-C8H10 + O2 -> A1CH3CH2-C8H9 + HO2 { A = 4.36E+07 n = 2.50 E = 192.65 }
2556 XY07f: A1CH3CH3-C8H10 + HO2 -> A1CH3CH2-C8H9 + H2O2 { A = 1.87E+05 n = 2.50 E = 61.44 }
2557 XY08f: A1CH3CH3-C8H10 + CH3 -> A1CH3CH2-C8H9 + CH4 { A = 9.03E-01 n = 3.65 E = 29.93 }
2558
2559 # From A1CH3+X (x2)
2560 XY09f: A1CH3CH3-C8H10 + H -> A1CH3-C7H8 + CH3 { A = 4.62E+06 n = 2.17 E = 17.42 }
2561 XY10f: A1CH3CH3-C8H10 + OH -> HOA1CH3-C7H8O + CH3 { A = 1.57E+03 n = 2.88 E = 13.48 }
2562
2563 # !!!! CAREFUL !!!!
2564 # Path from Bounaceur et al. 2005
2565 # Rate from A1+O (x2/3)
2566 XY11 : A1CH3CH3-C8H10 + O -> A1CH3-C7H8 + CO + 2H { A = 1.82E+08 n = 1.55 E = 12.93 }
2567
2568
2569 # Xylyl radical
2570 # -------------
2571
2572 # Path from Bournaceur et al. 2005
2573 # Rate from A1CH2
2574 XY12 : A1CH3CH2-C8H9 -> A1-C6H6 + H + C2H2 { A = 8.20E+14 n = .00 E = 337.55 }
2575
2576 XY13f: A1CH3CH2-C8H9 + H -> A1CH3*-C7H7 + CH3 { A = 5.83E+67 n =-14.15 E = 285.89 }
2577
2578 # From A1CH2+O
2579 XY14f: A1CH3CH2-C8H9 + O -> A1CH3CHO-C8H8O + H { A = 2.75E+13 n = 0.07 E = 3.06 }
2580 XY15f: A1CH3CH2-C8H9 + O -> A1CH3-C7H8 + HCO { A = 6.98E+12 n = 0.33 E = 2.87 }
2581
2582 # From A1CH2+O2
2583 # Addition from Murakami et al. 2009
2584 # Peroxy isomerization from Canneaux et al. 2008
2585 XY16f: A1CH3CH2-C8H9 + O2 -> A1CH3CHO-C8H8O + OH { A = 1.38E+02 n = 2.42 E = 31.13 }
2586
2587 # From A1CH2+HO2
2588 # Assumed unique decomposition into A1CHO+H
2589 XY19 : A1CH3CH2-C8H9 + HO2 -> A1CH3CHO-C8H8O + H + OH { A = 1.19E+09 n = 1.03 E = -9.41 }
2590
2591 # From A-C3H5 + C3H3
2592 XY20 : A1CH3CH2-C8H9 + C3H3 -> A2CH3-C11H10 + 2H { A = 1.88E+38 n = -7.53 E = 99.91 }
2593
2594
2595 # Tolualdehyde
2596 # ------------
2597
2598 # From A1CH3 & CH3CHO decomposition
2599 XY21f: A1CH3CHO-C8H8O -> A1CHOCH2-C8H7O + H { A = 1.56E+13 n = 0.68 E = 373.24 }
2600 XY22 : A1CH3CHO-C8H8O -> A1--C6H5 + CO + CH3 { A = 4.35E+22 n = -1.73 E = 436.01 }
2601 XY23 : A1CH3CHO-C8H8O -> A1CH3*-C7H7 + CO + H { A = 2.72E+22 n = -1.74 E = 361.33 }
2602
2603 # From A1CH3+R
2604 XY24f: A1CH3CHO-C8H8O + H -> A1CHOCH2-C8H7O + H2 { A = 6.47E+00 n = 3.98 E = 14.16 }
2605 XY25f: A1CH3CHO-C8H8O + O -> A1CHOCH2-C8H7O + OH { A = 9.50E+04 n = 2.68 E = 15.55 }
2606 XY26f: A1CH3CHO-C8H8O + OH -> A1CHOCH2-C8H7O + H2O { A = 1.77E+05 n = 2.39 E = -2.52 }
2607 XY27f: A1CH3CHO-C8H8O + CH3 -> A1CHOCH2-C8H7O + CH4 { A = 4.52E-01 n = 3.65 E = 29.93 }
2608
2609 # From CH3CHO+R
2610 XY28 : A1CH3CHO-C8H8O + H -> A1CH3*-C7H7 + CO + H2 { A = 1.31E+05 n = 2.58 E = 5.10 }
2611 XY29 : A1CH3CHO-C8H8O + O -> A1CH3*-C7H7 + CO + OH { A = 1.95E+13 n = .00 E = 14.81 }
2612 XY30 : A1CH3CHO-C8H8O + OH -> A1CH3*-C7H7 + CO + H2O { A = 9.70E+05 n = 2.11 E = -7.06 }
2613 XY31 : A1CH3CHO-C8H8O + CH3 -> A1CH3*-C7H7 + CO + CH4 { A = 1.55E+00 n = 3.70 E = 19.10 }
2614
2615
2616 # Tolualdehyde radical
2617 # --------------------
2618
2619 # From A1CH2+O
2620 XY32f: A1CHOCH2-C8H7O + O -> A1CHOCHO-C8H6O2 + H { A = 2.75E+13 n = 0.07 E = 3.06 }
2621 XY33f: A1CHOCH2-C8H7O + O -> A1CHO-C7H6O + HCO { A = 6.98E+12 n = 0.33 E = 2.87 }
2622
2623 # From A1CH2+HO2
2624 # Assumed unique decomposition into A1CHO+H
2625 XY33 : A1CHOCH2-C8H7O + HO2 -> A1CHOCHO-C8H6O2 + H + OH { A = 1.19E+09 n = 1.03 E = -9.41 }
2626
2627
2628 # Phthalaldehyde
2629 # --------------
2630
2631 # From CH3CHO decomposition (x2)
2632 XY34 : A1CHOCHO-C8H6O2 -> A1--C6H5 + 2 CO + H { A = 5.44E+22 n = -1.74 E = 361.33 }
2633
2634 # From CH3CHO+R (x2)
2635 XY35 : A1CHOCHO-C8H6O2 + H -> A1CHO-C7H6O + CO + H { A = 2.62E+05 n = 2.58 E = 5.10 }
2636 XY36 : A1CHOCHO-C8H6O2 + O -> A1CHO-C7H6O + CO + O { A = 3.90E+13 n = .00 E = 14.81 }
2637 XY37 : A1CHOCHO-C8H6O2 + OH -> A1CHO-C7H6O + CO + OH { A = 1.94E+06 n = 2.11 E = -7.06 }
2638 XY38 : A1CHOCHO-C8H6O2 + CH3 -> A1CHO-C7H6O + CO + CH3 { A = 3.10E+00 n = 3.70 E = 19.10 }
2639
2640
2641
2642 #==========================================================================#
2643 # #
2644 # Indene chemistry #
2645 # Adapted from Cyclopentadiene #
2646 # #
2647 #==========================================================================#
2648
2649
2650 # Indene
2651 # ------
2652
2653 # Kislov & Mebel 2007
2654 # Rate estimated
2655 I00f: A1--C6H5 + C3H3 -> C9H8 { A = 1.00E+13 n = .00 E = .00 }
2656
2657 # Kislov & Mebel 2007
2658 I01f: A1CH2-C7H7 + C2H2 -> C9H8 + H { A = 3.16E+04 n = 2.48 E = 46.28 }
2659
2660 I02f: C9H8 -> C9H7 + H { A = 3.24E+49 n =-10.01 E = 423.40 }
2661 I03f: C9H8 + H -> C9H7 + H2 { A = 8.59E+07 n = 1.85 E = 13.97 }
2662
2663 I05f: C9H8 + O -> C9H7 + OH { A = 4.77E+04 n = 2.71 E = 4.63 }
2664 I06f: C9H8 + OH -> C9H7 + H2O { A = 3.08E+06 n = 2.00 E = .00 }
2665 I07f: C9H8 + O2 -> C9H7 + HO2 { A = 1.00E+14 n = .00 E = 155.44 }
2666 I08f: C9H8 + HO2 -> C9H7 + H2O2 { A = 1.10E+04 n = 2.60 E = 53.97 }
2667 I09f: C9H8 + CH3 -> C9H7 + CH4 { A = 1.80E-01 n = 4.00 E = .00 }
2668
2669 # From C2H4 + O
2670 #I10 : C9H8 + O -> O-C6H4 + C2H3 + CO + H { A = 1.02E+08 n = 1.66 E = 2.75 }
2671
2672
2673 # Indenyl radical
2674 # 2/5 of the rate for C5H5
2675 # ------------------------
2676
2677 I12 : C9H7 + C5H5 -> A3-C14H10 + 2H { A = 2.56E+29 n = -4.03 E = 147.30 }
2678 I13 : C9H7 + CH3 -> A2-C10H8 + 2H { A = 1.96E+31 n = -4.85 E = 103.65 }
2679
2680 # TEST - GB
2681 #I14 : C9H7 -> C5H5 + C4H2 { A = 1.00E+10 n= .00 E = 250.00 }
2682
2683 I15 : C9H7 + O -> A1C2H2-C8H7 + CO { A = 5.08E+13 n = 0.26 E = 16.50 }
2684 I16 : C9H7 + OH -> A1C2H3-C8H8 + CO { A = 3.41E+13 n = 0.25 E = 18.20 }
2685 I17 : C9H7 + OH -> C9H6O + 2H { A = 4.44E+04 n = 1.90 E = 138.60 }
2686 I18 : C9H7 + O2 -> C9H6O + OH { A = 3.64E+15 n = -2.21 E = 10.20 }
2687 I19 : C9H7 + O2 -> C9H6O + O + H { A = 1.75E+03 n = 2.40 E = 211.50 }
2688 I20 : C9H7 + HO2 -> C9H6O + OH + H { A = 2.74E+13 n = 0.25 E = 21.30 }
2689
2690 # From A-C3H5 + C3H3
2691 I21 : C9H7 + C3H3 -> A2R5-C12H8 + 2H { A = 1.88E+38 n = -7.53 E = 99.91 }
2692
2693
2694 # Indenone
2695 # --------
2696
2697 I22 : C9H6O -> O-C6H4 + C2H2 + CO { A = 6.20E+41 n = -7.87 E = 413.00 }
2698
2699 I23 : C9H6O + H -> A1C2H2-C8H7 + CO { A = 1.37E+09 n = 1.46 E = 5.67 }
2700 I24 : C9H6O + O -> O-C6H4 + CH2CO + CO { A = 1.02E+08 n = 1.66 E = 2.75 }
2701
2702
2703
2704 #==========================================================================#
2705 # #
2706 # Napthalene Oxidation Chemistry #
2707 # Adapted from Benzene #
2708 # #
2709 #==========================================================================#
2710
2711 # Naphthalene
2712 # 5/3 of the rate for A1
2713 # ----------------------
2714
2715 NP01f: A2-C10H8 -> A2--C10H7 + H { A = 8.60E+60 n =-12.48 E = 619.55 }
2716 NP02f: A2-C10H8 + H -> A2--C10H7 + H2 { A = 4.01E+08 n = 1.80 E = 68.42 }
2717 NP03f: A2-C10H8 + OH -> A2--C10H7 + H2O { A = 3.90E+04 n = 2.68 E = 3.07 }
2718
2719 NP04f: A2-C10H8 -> A2*-C10H7 + H { A = 8.60E+60 n =-12.48 E = 619.55 }
2720 NP05f: A2-C10H8 + H -> A2*-C10H7 + H2 { A = 4.01E+08 n = 1.80 E = 68.42 }
2721 NP06f: A2-C10H8 + OH -> A2*-C10H7 + H2O { A = 3.90E+04 n = 2.68 E = 3.07 }
2722
2723 NP07f: A2-C10H8 + O -> A2O-C10H7O + H { A = 3.32E+07 n = 1.80 E = 16.63 }
2724 NP08f: A2-C10H8 + O -> A2OH-C10H8O { A = 2.55E+10 n = 0.92 E = 13.79 }
2725 NP09f: A2-C10H8 + O -> C9H8 + CO { A = 2.55E+17 n = -0.89 E = 64.89 }
2726
2727 NP10f: A2-C10H8 + OH -> A2OH-C10H8O + H { A = 2.20E+02 n = 3.25 E = 23.39 }
2728
2729
2730 # Naphthyl radical
2731 # Full rate for A1-
2732 # -----------------
2733
2734 # Park, Nguyen, Xu, Lin 2009
2735 NP11f: A2--C10H7 -> A2*-C10H7 { A = 1.51E+07 n = .00 E = 184.85 }
2736
2737 NP12f: A2--C10H7 + O2 -> A2O-C10H7O + O { A = 8.57E+20 n = -2.27 E = 30.08 }
2738 NP13f: A2*-C10H7 + O2 -> A2O-C10H7O + O { A = 8.57E+20 n = -2.27 E = 30.08 }
2739
2740 NP14 : A2--C10H7 + O2 -> C9H6O + CO + H { A = 3.00E+13 n = .00 E = 37.58 }
2741 NP15 : A2*-C10H7 + O2 -> C9H6O + CO + H { A = 3.00E+13 n = .00 E = 37.58 }
2742
2743 NP16f: A2--C10H7 + O -> A2O-C10H7O { A = 1.00E+14 n = .00 E = .00 }
2744 NP17f: A2*-C10H7 + O -> A2O-C10H7O { A = 1.00E+14 n = .00 E = .00 }
2745
2746 NP18f: A2--C10H7 + OH -> A2O-C10H7O + H { A = 3.00E+13 n = .00 E = .00 }
2747 NP19f: A2*-C10H7 + OH -> A2O-C10H7O + H { A = 3.00E+13 n = .00 E = .00 }
2748
2749
2750 # Naphthol
2751 # Full rate for A1OH
2752 # ------------------
2753
2754 NP20f: A2OH-C10H8O -> C9H8 + CO { A = 8.62E+15 n = -0.61 E = 310.11 }
2755 NP21f: A2OH-C10H8O -> A2O-C10H7O + H { A = 1.01E+71 n =-15.92 E = 522.12 }
2756
2757 NP22f: A2OH-C10H8O + H -> A2O-C10H7O + H2 { A = 6.83E+01 n = 3.40 E = 30.26 }
2758 NP23f: A2OH-C10H8O + OH -> A2O-C10H7O + H2O { A = 1.73E+01 n = 3.40 E = -4.78 }
2759 NP24f: A2OH-C10H8O + CH3 -> A2O-C10H7O + CH4 { A = 3.70E-04 n = 4.70 E = 20.20 }
2760
2761
2762 # Naphthoxy radical
2763 # Full rate for A1O
2764 # -----------------
2765
2766 NP25f: A2O-C10H7O -> C9H7 + CO { A = 2.90E+10 n = .00 E = 152.40 }
2767 NP26 : A2O-C10H7O + O -> C9H6O + CO + H { A = 1.68E+14 n = .00 E = .00 }
2768 NP27 : A2O-C10H7O + O2 -> C9H6O + CO + OH { A = 6.51E+07 n = 1.30 E = 73.92 }
2769
2770
2771
2772 #=========================================================================#
2773 # #
2774 # alpha-MethylNaphthalene chemistry #
2775 # Adapted from Toluene chemistry #
2776 # #
2777 #=========================================================================#
2778
2779
2780 # MethylNaphthalene
2781 # -----------------
2782
2783 MN01f: A2CH3-C11H10 + H -> A2-C10H8 + CH3 { A = 2.31E+06 n = 2.17 E = 17.42 }
2784 MN02f: A2CH3-C11H10 + OH -> A2OH-C10H8O + CH3 { A = 7.83E+02 n = 2.88 E = 13.48 }
2785
2786 # Collision Limit at 298K
2787 MN03f: A2CH3-C11H10 -> A2CH2-C11H9 + H { A = 1.25E+18 n = -0.60 E = 396.59 }
2788 MN04f: A2CH3-C11H10 -> A2--C10H7 + CH3 { A = 3.20E+34 n = -5.02 E = 478.03 }
2789
2790 MN05f: A2CH2-C11H9 + H -> A2--C10H7 + CH3 { A = 5.83E+67 n =-14.15 E = 285.89 }
2791 MN06f: A2CH2-C11H9 -> C9H7 + C2H2 { A = 8.20E+14 n = .00 E = 337.55 }
2792
2793 MN07f: A2CH3-C11H10 + H -> A2CH2-C11H9 + H2 { A = 6.47E+00 n = 3.98 E = 14.16 }
2794 MN08f: A2CH3-C11H10 + O -> A2CH2-C11H9 + OH { A = 1.18E+00 n = 4.09 E = 10.65 }
2795 MN09f: A2CH3-C11H10 + OH -> A2CH2-C11H9 + H2O { A = 1.77E+05 n = 2.39 E = -2.52 }
2796 MN10f: A2CH3-C11H10 + O2 -> A2CH2-C11H9 + HO2 { A = 2.18E+07 n = 2.50 E = 192.65 }
2797 MN11f: A2CH3-C11H10 + CH3 -> A2CH2-C11H9 + CH4 { A = 1.73E+01 n = 3.44 E = 43.47 }
2798 MN12f: A2CH3-C11H10 + HO2 -> A2CH2-C11H9 + H2O2 { A = 9.33E+04 n = 2.50 E = 61.44 }
2799
2800 MN13 : A2CH3-C11H10 + O -> A2-C10H8 + CO + 2 H { A = 1.10E+13 n = .00 E = 18.96 }
2801 MN14 : A2CH3-C11H10 + O -> C9H7 + CH3 + CO { A = 1.47E+13 n = .00 E = 18.96 }
2802
2803
2804 # Methylene-Naphthyl
2805 # ------------------
2806
2807 MN15f: A2CH2-C11H9 + O -> A2-C10H8 + HCO { A = 6.98E+12 n = 0.33 E = 2.87 }
2808 MN16f: A2CH2-C11H9 + O -> A2CHO-C11H8O + H { A = 2.75E+13 n = 0.07 E = 3.06 }
2809 MN17f: A2CH2-C11H9 + O2 -> A2CHO-C11H8O + OH { A = 3.76E+15 n = -1.55 E = 47.37 }
2810 MN18f: A2CH2-C11H9 + HO2 -> A2CH2O-C11H9O + OH { A = 1.19E+09 n = 1.03 E = -9.41 }
2811
2812 MN19 : A2CH2-C11H9 + C3H3 -> A3-C14H10 + 2H { A = 1.88E+38 n = -7.53 E = 99.91 }
2813
2814
2815 # Methoxy-Naphthyl
2816 # ----------------
2817
2818 MN20f: A2CH2O-C11H9O -> A2CHO-C11H8O + H { A = 1.27E+13 n = .00 E = 86.19 }
2819 MN21f: A2CH2O-C11H9O -> A2--C10H7 + CH2O { A = 7.21E+33 n = -6.21 E = 154.18 }
2820
2821 MN22f: A2CH2O-C11H9O + H -> A2CHO-C11H8O + H2 { A = 1.33E+13 n = .00 E = .00 }
2822 MN23f: A2CH2O-C11H9O + O -> A2CHO-C11H8O + OH { A = 6.67E+12 n = .00 E = .00 }
2823 MN24f: A2CH2O-C11H9O + OH -> A2CHO-C11H8O + H2O { A = 3.33E+12 n = .00 E = .00 }
2824 MN25f: A2CH2O-C11H9O + O2 -> A2CHO-C11H8O + HO2 { A = 4.11E+10 n = .00 E = 7.32 }
2825
2826
2827 # Naphthaldehyde
2828 # --------------
2829
2830 MN26 : A2CHO-C11H8O -> A2--C10H7 + CO + H { A = 2.72E+22 n = -1.74 E = 361.33 }
2831
2832 MN27 : A2CHO-C11H8O + H -> A2--C10H7 + CO +H2 { A = 1.31E+05 n = 2.58 E = 5.10 }
2833 MN28 : A2CHO-C11H8O + O -> A2--C10H7 + CO +OH { A = 1.95E+13 n = .00 E = 14.81 }
2834 MN29 : A2CHO-C11H8O + OH -> A2--C10H7 + CO +H2O { A = 9.70E+05 n = 2.11 E = -7.06 }
2835 MN30 : A2CHO-C11H8O + CH3-> A2--C10H7 + CO +CH4 { A = 1.55E+00 n = 3.70 E = 19.10 }
2836
2837
2838
2839 #==========================================================================#
2840 # #
2841 # PAH chemistry #
2842 # HACA Based Mechanism #
2843 # #
2844 #==========================================================================#
2845
2846 # Fulvene
2847 # -------
2848
2849 # Jasper & Hansen 2013 - 1atm
2850 P01f: C5H4CH2 + H -> A1-C6H6 + H { A = 1.14E+32 n = -4.88 E = 79.05 }
2851
2852 # Senosiain & Miller 2007 (JPCA)
2853 P02f: N-C4H5 + C2H2 -> C5H4CH2 + H { A = 4.62E+15 n = -0.89 E = 38.25 }
2854 P03f: I-C4H5 + C2H2 -> C5H4CH2 + H { A = 6.80E+24 n = -3.45 E = 85.09 }
2855
2856 # Miller & Klippenstein 2003
2857 P04f: C5H4CH2 -> A1-C6H6 { A = 1.45E+45 n = -8.90 E = 405.86 }
2858 P05f: C5H4CH2 -> A1--C6H5 + H { A = 2.24E+68 n =-14.65 E = 596.54 }
2859
2860
2861 # Benzene
2862 # -------
2863
2864 # Wang & Frenklach 1997
2865 P06f: N-C4H3 + C2H2 -> A1--C6H5 { A = 9.60E+70 n =-17.77 E = 130.96 }
2866
2867 # Senosiain & Miller 2007 (JPCA)
2868 P07f: N-C4H5 + C2H2 -> A1-C6H6 + H { A = 1.38E+16 n = -1.00 E = 37.24 }
2869 P08f: I-C4H5 + C2H2 -> A1-C6H6 + H { A = 1.67E+23 n = -3.30 E = 104.43 }
2870
2871 # Miller, Klippenstein, Georgievskii, Harding, Allen, Simmonett 2010
2872 P09 : A-C3H5 + C3H3 -> C5H4CH2 + 2H { A = 1.88E+38 n = -7.53 E = 99.91 }
2873
2874 # Georgievskii, Miller, & Klippenstein 2007
2875 # -> Total rate at 1bar
2876 # Miller & Klippenstein 2003
2877 # -> Branching ratios
2878 # -> 2-ethynyl-1,3-butadiene lumped into Fulvene
2879 # Fitted rates valid for 800K-2000K - P=1bar
2880 P10f: C3H3 + C3H3 -> C5H4CH2 { A = 8.25E+46 n =-10.10 E = 70.96 }
2881 P11f: C3H3 + C3H3 -> A1-C6H6 { A = 1.07E+45 n = -9.57 E = 71.19 }
2882 P12f: C3H3 + C3H3 -> A1--C6H5 + H { A = 5.77E+37 n = -7.00 E = 131.82 }
2883
2884 # Tokmakov & Lin 2004
2885 P13f: A1--C6H5 + C2H4 -> A1-C6H6 + C2H3 { A = 9.45E-03 n = 4.47 E = 18.71 }
2886
2887
2888 # Naphthalene
2889 # -----------
2890
2891 # From A1 (x1/3)
2892 P14f: A1C2H-C8H6 + C2H -> A2--C10H7 { A = 6.67E+13 n = .00 E = .00 }
2893 P15f: A1C2H3-C8H8 + C2H -> A2-C10H8 + H { A = 6.67E+13 n = .00 E = .00 }
2894
2895 # Kislov & Mebel 2005
2896 P16f: A1C2H*-C8H5 + C2H2 -> A2--C10H7 { A = 1.34E+04 n = 2.50 E = 5.37 }
2897 P17f: A1C2H2-C8H7 + C2H2 -> A2-C10H8 + H { A = 2.62E+06 n = 2.00 E = 19.16 }
2898 P18f: A1C2H3*-C8H7 + C2H2 -> A2-C10H8 + H { A = 3.02E+03 n = 2.55 E = 13.31 }
2899
2900 # From A1 (x1/3)
2901 P19f: A1C2H-C8H6 + C2H3 -> A2-C10H8 + H { A = 4.50E+16 n = -1.15 E = 61.01 }
2902
2903 # From A1-
2904 P20f: A1C2H*-C8H5 + C2H4 -> A2-C10H8 + H { A = 3.62E+28 n = -4.24 E = 99.85 }
2905
2906 # Aguilera-Iparraguirre & Klopper 2007
2907 # Total entrance channel rate
2908 P21f: A1--C6H5 + C4H4 -> A2-C10H8 + H { A = 1.26E+04 n = 2.61 E = 6.00 }
2909
2910
2911 # From A1 (x2/3)
2912 P22f: A2-C10H8 + C2H -> A2C2HA-C12H8 + H { A = 1.67E+14 n = .00 E = .00 }
2913 P23f: A2-C10H8 + C2H -> A2C2HB-C12H8 + H { A = 1.67E+14 n = .00 E = .00 }
2914
2915 # Park, Nguyen, Xu, Lin 2009
2916 P24f: A2--C10H7 + C2H2 -> A2R5-C12H8 + H { A = 2.81E+07 n = 1.77 E = 9.37 }
2917 P25f: A2*-C10H7 + C2H2 -> A2C2HB-C12H8 + H { A = 5.38E+07 n = 1.65 E = 10.71 }
2918
2919 # From A1 (x2/3)
2920 P26f: A2-C10H8 + C2H3 -> A2C2H2A-C12H9 + H2 { A = 9.01E+16 n = -1.15 E = 61.01 }
2921 P27f: A2-C10H8 + C2H3 -> A2C2H2B-C12H9 + H2 { A = 9.01E+16 n = -1.15 E = 61.01 }
2922
2923 # From A1-
2924 P28f: A2--C10H7 + C2H4 -> A2C2H2A-C12H9 + H2 { A = 3.62E+28 n = -4.24 E = 99.85 }
2925 P29f: A2*-C10H7 + C2H4 -> A2C2H2B-C12H9 + H2 { A = 3.62E+28 n = -4.24 E = 99.85 }
2926
2927
2928 # From A1C2H2
2929 P30f: A2C2H2A-C12H9 -> A2C2HA-C12H8 + H { A = 1.81E+54 n =-12.69 E = 215.02 }
2930 P31f: A2C2H2A-C12H9 + H -> A2C2HA-C12H8 + H2 { A = 1.50E+13 n = .00 E = .00 }
2931 P32f: A2C2H2A-C12H9 + OH -> A2C2HA-C12H8 + H2O { A = 2.50E+12 n = .00 E = .00 }
2932
2933 P33f: A2C2H2B-C12H9 -> A2C2HB-C12H8 + H { A = 1.81E+54 n =-12.69 E = 215.02 }
2934 P34f: A2C2H2B-C12H9 + H -> A2C2HB-C12H8 + H2 { A = 1.50E+13 n = .00 E = .00 }
2935 P35f: A2C2H2B-C12H9 + OH -> A2C2HB-C12H8 + H2O { A = 2.50E+12 n = .00 E = .00 }
2936
2937 # From A1 (x1/6)
2938 P36f: A2C2HA-C12H8 -> A2C2HA*-C12H7 + H { A = 2.15E+60 n =-12.48 E = 619.55 }
2939 P37f: A2C2HA-C12H8 + H -> A2C2HA*-C12H7 + H2 { A = 1.00E+08 n = 1.80 E = 68.42 }
2940 P38f: A2C2HA-C12H8 + OH -> A2C2HA*-C12H7 + H2O { A = 3.90E+03 n = 2.68 E = 3.07 }
2941
2942 P39f: A2C2HB-C12H8 -> A2C2HB*-C12H7 + H { A = 2.15E+60 n =-12.48 E = 619.55 }
2943 P40f: A2C2HB-C12H8 + H -> A2C2HB*-C12H7 + H2 { A = 1.00E+08 n = 1.80 E = 68.42 }
2944 P41f: A2C2HB-C12H8 + OH -> A2C2HB*-C12H7 + H2O { A = 3.90E+03 n = 2.68 E = 3.07 }
2945
2946
2947 # Acenaphthalene
2948 # --------------
2949
2950 # Kislov & Mebel 2005
2951 P42f: A2C2H2A-C12H9 -> A2R5-C12H8 + H { A = 2.88E+11 n = 0.23 E = 71.24 }
2952
2953 # Lifshitz, Tambura & Dubnikova 2007
2954 P43f: A2C2HA-C12H8 + H -> A2R5-C12H8 + H { A = 3.52E+12 n = .00 E = 55.90 }
2955
2956 # From A1 (x2/3)
2957 P44f: A2R5-C12H8 -> A2R5--C12H7 + H { A = 8.60E+60 n =-12.48 E = 619.55 }
2958 P45f: A2R5-C12H8 + H -> A2R5--C12H7 + H2 { A = 4.01E+08 n = 1.80 E = 68.42 }
2959 P46f: A2R5-C12H8 + OH -> A2R5--C12H7 + H2O { A = 1.34E+04 n = 2.68 E = 3.07 }
2960
2961
2962 # From A1 (x2/3)
2963 P47f: A2R5-C12H8 + C2H -> A2R5C2H-C14H8 + H { A = 1.67E+14 n = .00 E = .00 }
2964
2965 # From A2*
2966 P48f: A2R5--C12H7 + C2H2 -> A2R5C2H-C14H8 + H { A = 5.38E+07 n = 1.65 E = 10.71 }
2967
2968 # From A1 (x2/3)
2969 P49f: A2R5-C12H8 + C2H3 -> A2R5C2H2-C14H9 + H2 { A = 9.01E+16 n = -1.15 E = 61.01 }
2970
2971 # From A1-
2972 P50f: A2R5--C12H7 + C2H4 -> A2R5C2H2-C14H9 + H2 { A = 3.62E+28 n = -4.24 E = 99.85 }
2973
2974
2975 # From A1C2H2
2976 P51f: A2R5C2H2-C14H9 -> A2R5C2H-C14H8 + H { A = 2.09E+38 n = -7.74 E = 196.19 }
2977 P52f: A2R5C2H2-C14H9 + H -> A2R5C2H-C14H8 + H2 { A = 1.65E+11 n = 0.49 E = 44.48 }
2978 P53f: A2R5C2H2-C14H9 + OH-> A2R5C2H-C14H8 + H2O { A = 2.50E+12 n = .00 E = .00 }
2979
2980 # From A1 (x1/6)
2981 P54f: A2R5C2H-C14H8 -> A2R5C2H*-C14H7 + H { A = 2.15E+60 n =-12.48 E = 619.55 }
2982 P55f: A2R5C2H-C14H8 + H -> A2R5C2H*-C14H7 + H2 { A = 1.00E+08 n = 1.80 E = 68.42 }
2983 P56f: A2R5C2H-C14H8 + OH-> A2R5C2H*-C14H7 + H2O { A = 3.90E+03 n = 2.68 E = 3.07 }
2984
2985
2986 # Biphenyl
2987 # --------
2988
2989 # Park, Burova,, Rodgers & Lin 1999
2990 # Fitted exp rate
2991 P57f: A1-C6H6 + A1--C6H5 -> P2-C12H10 + H { A = 9.55E+11 n = .00 E = 9.07 }
2992
2993 # Tranter, Klippenstein, Harding, Giri, Yang, Keifer 2010
2994 P58f: A1--C6H5 + A1--C6H5 -> P2-C12H10 { A = 7.34E+20 n = -2.34 E = 17.26 }
2995 P59f: A1--C6H5 + A1--C6H5 -> P2--C12H9 + H { A = 2.44E+13 n = 0.89 E = 180.66 }
2996
2997 # From A1 (x2/3)
2998 P60f: P2-C12H10 -> P2--C12H9 + H { A = 8.60E+60 n =-12.48 E = 619.55 }
2999 P61f: P2-C12H10 + H -> P2--C12H9 + H2 { A = 4.01E+08 n = 1.80 E = 68.42 }
3000 P62f: P2-C12H10 + OH -> P2--C12H9 + H2O { A = 1.34E+04 n = 2.68 E = 3.07 }
3001
3002
3003 # Phenanthrene
3004 # ------------
3005
3006 # From A1C2H3*
3007 P63f: P2--C12H9 + C2H2 -> A3-C14H10 + H { A = 3.02E+03 n = 2.55 E = 13.31 }
3008
3009 # From P2 (x1/3)
3010 P64f: A1C2H-C8H6 + A1--C6H5 -> A3-C14H10 + H { A = 3.18E+11 n = .00 E = 9.07 }
3011 # From P2 & P2-
3012 P65f: A1C2H*-C8H5 + A1-C6H6 -> A3-C14H10 + H { A = 9.55E+11 n = .00 E = 9.07 }
3013 P66f: A1C2H*-C8H5 + A1--C6H5 -> A3-C14H10 { A = 1.39E+13 n = .00 E = 0.47 }
3014
3015
3016 # From A1 (x1/6)
3017 P67f: A2C2HA-C12H8 + C2H -> A3--C14H9 { A = 3.33E+13 n = .00 E = .00 }
3018 P68f: A2C2HB-C12H8 + C2H -> A3--C14H9 { A = 3.33E+13 n = .00 E = .00 }
3019
3020 # From A1C2H*
3021 P69f: A2C2HA*-C12H7 + C2H2 -> A3*-C14H9 { A = 1.34E+04 n = 2.50 E = 5.37 }
3022 P70f: A2C2HB*-C12H7 + C2H2 -> A3*-C14H9 { A = 1.34E+04 n = 2.50 E = 5.37 }
3023
3024 # From A1C2H2
3025 P71f: A2C2H2A-C12H9 + C2H2 -> A3-C14H10 + H { A = 2.62E+06 n = 2.00 E = 19.16 }
3026 P72f: A2C2H2B-C12H9 + C2H2 -> A3-C14H10 + H { A = 2.62E+06 n = 2.00 E = 19.16 }
3027
3028 # From A1 (x1/6)
3029 P73f: A2C2HA-C12H8 + C2H3 -> A3-C14H10 + H { A = 2.25E+16 n = -1.15 E = 61.01 }
3030 P74f: A2C2HB-C12H8 + C2H3 -> A3-C14H10 + H { A = 2.25E+16 n = -1.15 E = 61.01 }
3031
3032 # From A1-
3033 P75f: A2C2HA*-C12H7 + C2H4 -> A3-C14H10 + H { A = 3.62E+28 n = -4.24 E = 99.85 }
3034 P76f: A2C2HB*-C12H7 + C2H4 -> A3-C14H10 + H { A = 3.62E+28 n = -4.24 E = 99.85 }
3035
3036 # From A1-
3037 P77f: A2--C10H7 + C4H4 -> A3-C14H10 + H { A = 1.26E+04 n = 2.61 E = 6.00 }
3038 P78f: A2*-C10H7 + C4H4 -> A3-C14H10 + H { A = 1.26E+04 n = 2.61 E = 6.00 }
3039
3040
3041 # From A1 (x1/3)
3042 P79f: A3-C14H10 -> A3*-C14H9 + H { A = 4.30E+60 n =-12.48 E = 619.55 }
3043 P80f: A3-C14H10 + H -> A3*-C14H9 + H2 { A = 2.00E+08 n = 1.80 E = 68.42 }
3044 P81f: A3-C14H10 + OH -> A3*-C14H9 + H2O { A = 7.80E+03 n = 2.68 E = 3.07 }
3045
3046 # From A1 (x2/3)
3047 P82f: A3-C14H10 -> A3--C14H9 + H { A = 8.60E+60 n =-12.48 E = 619.55 }
3048 P83f: A3-C14H10 + H -> A3--C14H9 + H2 { A = 4.01E+08 n = 1.80 E = 68.42 }
3049 P84f: A3-C14H10 + OH -> A3--C14H9 + H2O { A = 1.56E+04 n = 2.68 E = 3.07 }
3050
3051 # Frenklach 2005
3052 P85f: A3*-C14H9 -> A2R5--C12H7 + C2H2 { A = 1.30E+11 n = 1.08 E = 294.55 }
3053
3054
3055 # Acephenanthrylene
3056 # -----------------
3057
3058 # From A1C2H*
3059 P86f: A2R5C2H*-C14H7 + C2H2 -> A3R5--C16H9 { A = 1.34E+04 n = 2.50 E = 5.37 }
3060
3061 # From A1C2H2
3062 P87f: A2R5C2H2-C14H9 + C2H2 -> A3R5-C16H10 + H { A = 2.62E+06 n = 2.00 E = 19.16 }
3063
3064 # From A2-
3065 P88f: A3--C14H9 + C2H2 -> A3R5-C16H10 + H { A = 2.81E+07 n = 1.77 E = 9.37 }
3066
3067 # From A1-
3068 P89f: A2R5--C12H7 + C4H4 -> A3R5-C16H10 + H { A = 1.26E+04 n = 2.61 E = 6.00 }
3069
3070
3071 # From A1 (x1/3)
3072 P90f: A3R5-C16H10 -> A3R5--C16H9 + H { A = 2.15E+60 n =-12.48 E = 619.55 }
3073 P91f: A3R5-C16H10 + H -> A3R5--C16H9 + H2 { A = 2.01E+08 n = 1.80 E = 68.42 }
3074 P92f: A3R5-C16H10 + OH -> A3R5--C16H9 + H2O { A = 7.80E+03 n = 2.68 E = 3.07 }
3075
3076
3077 # Pyrene
3078 # ------
3079
3080 # From A2*
3081 P93f: A3*-C14H9 + C2H2 -> A4-C16H10 + H { A = 5.38E+07 n = 1.65 E = 10.71 }
3082
3083 # From A1 (x4/3)
3084 P94f: A4-C16H10 -> A4--C16H9 + H { A = 1.72E+60 n =-12.48 E = 619.55 }
3085 P95f: A4-C16H10 + H -> A4--C16H9 + H2 { A = 8.03E+08 n = 1.80 E = 68.42 }
3086 P96f: A4-C16H10 + OH -> A4--C16H9 + H2O { A = 3.12E+04 n = 2.68 E = 3.07 }
3087
3088
3089 # Cyclopenta[cd]pyrene
3090 # --------------------
3091
3092 # From A2-/A2*
3093 P97f: A4--C16H9 + C2H2 -> A4R5-C18H10 + H { A = 2.81E+07 n = 1.77 E = 9.37 }
3094 P98f: A3R5--C16H9 + C2H2 -> A4R5-C18H10 + H { A = 5.38E+07 n = 1.65 E = 10.71 }
3095
3096
3097 # Fluoranthene
3098 # ------------
3099
3100 # From A1+A1- (x2/3 and x1)
3101 P99 : A2-C10H8 + A1--C6H5 -> FLTN-C16H10 + H2+H { A = 6.37E+11 n = .00 E = 9.07 }
3102 P100: A2--C10H7 + A1-C6H6 -> FLTN-C16H10 + H2+H { A = 9.55E+11 n = .00 E = 9.07 }
3103
3104 # From A1-+A1-
3105 P101: A2--C10H7 + A1--C6H5 -> FLTN-C16H10 + 2H { A = 1.39E+13 n = .00 E = 0.47 }
3106
3107
3108
3109 #==========================================================================#
3110 # #
3111 # Higher PAH Oxidation Chemistry #
3112 # Adapted from Benzene #
3113 # #
3114 #==========================================================================#
3115
3116 # From A1-+O2
3117 OX01 : A3*-C14H9 + O2 -> A2C2H2B-C12H9 + 2CO { A = 8.57E+20 n = -2.27 E = 30.08 }
3118 OX02 : A3--C14H9 + O2 -> A2C2H2A-C12H9 + 2CO { A = 8.57E+20 n = -2.27 E = 30.08 }
3119 OX03 : A4--C16H9 + O2 -> A3*-C14H9 + 2CO { A = 8.57E+20 n = -2.27 E = 30.08 }
3120 OX04 : A2R5--C12H7 + O2 -> A2--C10H7 + 2CO { A = 8.57E+20 n = -2.27 E = 30.08 }
3121 OX05 : A3R5--C16H9 + O2 -> A3*-C14H9 + 2CO { A = 8.57E+20 n = -2.27 E = 30.08 }
3122
3123 # From A1+OH
3124 # Rescaled by number of active sites
3125 OX06 : A3-C14H10 + OH -> A2C2HA-C12H8 +CH3+CO { A = 1.10E+02 n = 3.25 E = 23.39 }
3126 OX07 : A3-C14H10 + OH -> A2C2HB-C12H8 +CH3+CO { A = 1.10E+02 n = 3.25 E = 23.39 }
3127 OX08 : A4-C16H10 + OH -> A3-C14H10 + HCCO { A = 2.20E+02 n = 3.25 E = 23.39 }
3128 OX09 : A2R5-C12H8 + OH -> A2-C10H8 + HCCO { A = 1.76E+02 n = 3.25 E = 23.39 }
3129 OX10 : A3R5-C16H10 + OH -> A3-C14H10 + HCCO { A = 2.20E+02 n = 3.25 E = 23.39 }
3130 OX11 : A4R5-C18H10 + OH -> A4-C16H10 + HCCO { A = 2.20E+02 n = 3.25 E = 23.39 }
3131 OX12 : FLTN-C16H10 + OH -> A3-C14H10 + HCCO { A = 2.20E+02 n = 3.25 E = 23.39 }
3132
3133
3134
3135 #================================================================#
3136 # #
3137 # Soot Formation #
3138 # #
3139 #================================================================#
3140
3141 ###### H-Abstraction ######
3142
3143 # Tokmakov & Lin 1999/2002
3144 # Rates indep of pressure
3145 # 1/6 of forward and full backward
3146 SOOT1f: Soot-CH + OH -> Soot-C + H2O { A = 6.72E+01 n = 3.33 E = 6.09 }
3147 SOOT1b: Soot-C + H2O -> Soot-CH + OH { A = 6.44E-01 n = 3.79 E = 27.96 }
3148
3149 # Mebel & Lin 1997
3150 # Rates indep of pressure
3151 # 1/6 of forward and full backward
3152 SOOT2f: Soot-CH + H -> Soot-C + H2 { A = 1.00E+08 n = 1.80 E = 68.42 }
3153 SOOT2b: Soot-C + H2 -> Soot-CH + H { A = 8.68E+04 n = 2.36 E = 25.46 }
3154
3155 # Harding, Georgievskii & Klippenstein 2005
3156 # High Pressure Limit
3157 # 1/6 of forward and full backward
3158 SOOT3f: Soot-CH -> Soot-C + H { A = 1.13E+16 n = -0.06 E = 476.05 }
3159 SOOT3b: Soot-C + H -> Soot-CH { A = 4.17E+13 n = 0.15 E = .00 }
3160
3161
3162 ###### C2H2-Addition ######
3163
3164 # Tokmakov & Lin 2004
3165 # High pressure rates for A1- + C2H2 <=> A1C2H2 (x2)
3166 SOOT4: Soot-C + C2H2 -> Soot-CH noCheck { A = 2.52E+09 n = 1.10 E = 17.13 }
3167
3168
3169 ###### Oxidation ######
3170
3171 # Assume first reaction step is the limiting step:
3172 # Attack by O2 or OH
3173
3174 # Kazakov, Wang & Frenklach 1995
3175 SOOT5: Soot-C + O2 -> Soot-C + 2CO noCheck { A = 2.20E+12 n = .00 E = 31.38 }
3176
3177 # Sarofim 1981
3178 # Directly Coded in FlameMaster
3179 # From collision efficiency - 0.13
3180 SOOT6 : Soot-CH + OH -> Soot-C + CO noCheck { A = 0.00E+00 n = .00 E = .00 }
3181
3182
3183 # **** Third Body *****
3184
3185 Let M0 = 1.0 [OTHER].
3186
3187 Let M1 = 0.0 [H2] + 0.0 [H2O] + 0.63 [AR] + 0.00 [CO2] + 1.0 [OTHER].
3188 Let M2 = 2.5 [H2] + 12.0 [H2O] + 0.75 [AR] + 1.0 [OTHER].
3189 Let M3 = 2.5 [H2] + 12.0 [H2O] + 0.00 [AR] + 1.0 [OTHER].
3190 Let M4 = 1.5 [H2] + 11.7 [H2O] + 0.52 [AR] + 1.09 [CO] + 2.18 [CO2] + 0.89 [O2] + 1.0 [OTHER].
3191 Let M5 = 3.0 [H2] + 0.0 [H2O] + 2.00 [N2] + 1.50 [O2] + 1.0 [OTHER].
3192 Let M6 = 2.5 [H2] + 9.0 [H2O] + 1.50 [N2] + 1.0 [OTHER].
3193
3194 Let M7 = 2.0 [H2] + 12.0 [H2O] + 0.70 [AR] + 1.75 [CO] + 3.60 [CO2] + 1.0 [OTHER].
3195 Let M8 = 2.0 [H2] + 0.0 [H2O] + 1.75 [CO] + 3.60 [CO2] + 1.0 [OTHER].
3196
3197 Let M9 = 2.0 [H2] + 6.0 [H2O] + 0.70 [AR] + 1.50 [CO] + 2.00 [CO2] + 2 [CH4] + 3 [C2H6] + 1.0 [OTHER].
3198
3199 Let M10= 2.5 [H2] + 16.3 [H2O] + 0.88 [AR] + 1.0 [OTHER].

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