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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 # Chemistry of excited OH and CH states #
121 # de Vries, Hall, Simmons, Rickard, Kalitan, Petersen 2007 #
122 # (simplified) #
123 # #
124 #=========================================================================#
125
126
127 # Excited OH*
128 # -----------
129
130 E01f: S-OH -> OH { A = 1.40E+06 n = .00 E = .00 }
131 E02f: S-OH + M0 -> OH + M0 { A = 2.17E+10 n = 0.50 E = 8.62 }
132 E03f: S-OH + O2 -> OH + O2 { A = 2.10E+12 n = 0.50 E = -2.02 }
133
134 E04f: O + H + M0 -> S-OH + M0 { A = 3.10E+14 n = .00 E = 41.84 }
135 E05f: CH + O2 -> S-OH + CO { A = 3.24E+14 n = -0.40 E = 17.36 }
136
137
138 # Excited CH*
139 # -----------
140
141 E06f: S-CH -> CH { A = 1.86E+06 n = .00 E = .00 }
142 E07f: S-CH + M0 -> CH + M0 { A = 4.00E+10 n = 0.50 E = .00 }
143 E08f: S-CH + O2 -> CH + O2 { A = 2.48E+06 n = 2.14 E = -7.20 }
144
145 E09f: C + H + M0 -> S-CH + M0 { A = 3.63E+13 n = .00 E = .00 }
146 E10f: C2H + O -> S-CH + CO { A = 5.20E+11 n = .00 E = 10.88 }
147
148 # Elsamra, Vranckx, Carl 2005
149 E11f: C2H + O2 -> S-CH + CO2 { A = 6.02E-04 n = 4.40 E = -9.56 }
150
151
152
153 #=========================================================================#
154 # #
155 # GRI-MECH version 3.0 #
156 # http://www.me.berkeley.edu/gri_mech/ #
157 # #
158 # Gregory P. Smith, David M. Golden, Michael Frenklach, Nigel W. Moriarty #
159 # Boris Eiteneer, Mikhail Goldenberg, C. Thomas Bowman, Ronald K. Hanson, #
160 # Soonho Song, William C. Gardiner, Jr., Vitali V. Lissianski, Zhiwei Qin #
161 # #
162 #=========================================================================#
163
164 # Carbon
165 # ------
166
167 G01f: C + OH -> CO + H { A = 5.00E+13 n = .00 E = .00 }
168 G02f: C + O2 -> CO + O { A = 5.80E+13 n = .00 E = 2.41 }
169
170
171 # Methylidyne
172 # -----------
173
174 # Back to value before GRI opt
175 # Dean, Davidson, Hanson 1991
176 G03f: CH + H -> C + H2 { A = 1.10E+14 n = .00 E = .00 }
177
178 G04f: CH + O -> CO + H { A = 5.70E+13 n = .00 E = .00 }
179 G05f: CH + OH -> HCO + H { A = 3.00E+13 n = .00 E = .00 }
180 G06f: CH + H2 -> T-CH2 + H { A = 1.08E+14 n = .00 E = 13.01 }
181 G07f: CH + H2 + M9 -> CH3 + M9 { A = 4.82E+25 n = -2.80 E = 2.47
182 Ai= 1.97E+12 ni= 0.43 Ei= -1.55
183 fcA = 0.422 fctA = 122
184 fcb = 0.578 fctb = 2535
185 fcc = 1.0 fctc = 9365 }
186 G08f: CH + H2O -> CH2O + H { A = 5.71E+12 n = .00 E = -3.16 }
187 G09f: CH + O2 -> HCO + O { A = 6.71E+13 n = .00 E = .00 }
188 G10f: CH + CO + M9 -> HCCO + M9 { A = 2.69E+28 n = -3.74 E = 8.10
189 Ai= 5.00E+13 ni= .00 Ei= .00
190 fcA = 0.4243 fctA = 237
191 fcb = 0.5757 fctb = 1652
192 fcc = 1.0 fctc = 5069 }
193 G11f: CH + CO2 -> HCO + CO { A = 1.90E+14 n = .00 E = 66.07 }
194
195
196 # Carbon oxides
197 # -------------
198
199 G12f: CO + H2 + M9 -> CH2O + M9 { A = 5.07E+27 n = -3.42 E = 352.92
200 Ai= 4.30E+07 ni= 1.50 Ei= 333.05
201 fcA = 0.068 fctA = 197
202 fcb = 0.932 fctb = 1540
203 fcc = 1.0 fctc = 10300 }
204 G13f: HCO + H + M9 -> CH2O + M9 { A = 2.47E+24 n = -2.57 E = 1.78
205 Ai= 1.09E+12 ni= .48 Ei= -1.09
206 fcA = 0.2176 fctA = 271
207 fcb = 0.7824 fctb = 2755
208 fcc = 1.0 fctc = 6570 }
209
210
211 # Methylene (triplet)
212 # -------------------
213
214 G14f: T-CH2 + H + M9 -> CH3 + M9 { A = 1.04E+26 n = -2.76 E = 6.69
215 Ai= 6.00E+14 ni= .00 Ei= .00
216 fcA = 0.438 fctA = 91
217 fcb = 0.562 fctb = 5836
218 fcc = 1.0 fctc = 8552 }
219 G15f: T-CH2 + O -> HCO + H { A = 8.00E+13 n = .00 E = .00 }
220 G16f: T-CH2 + OH -> CH2O + H { A = 2.00E+13 n = .00 E = .00 }
221 G17f: T-CH2 + OH -> CH + H2O { A = 1.13E+07 n = 2.00 E = 12.55 }
222 G18f: T-CH2 + H2 -> CH3 + H { A = 5.00E+05 n = 2.00 E = 30.25 }
223
224 # Alvarez, Moore, 1994
225 # Lee, Matsui, Chen, Wang 2012
226 # (revised branching ratios 0.58/0.20/0.22)
227 G19f: T-CH2 + O2 -> HCO + OH { A = 9.57E+12 n = .00 E = 7.27 }
228 G20f: T-CH2 + O2 -> CH2O + O { A = 3.30E+12 n = .00 E = 7.27 }
229 G21f: T-CH2 + O2 -> CO2 + H2 { A = 3.63E+12 n = .00 E = 7.27 }
230
231 G22f: T-CH2 + HO2 -> CH2O + OH { A = 2.00E+13 n = .00 E = .00 }
232 G23f: T-CH2 + C -> C2H + H { A = 5.00E+13 n = .00 E = .00 }
233 G24f: T-CH2 + CO + M9 -> CH2CO + M9 { A = 2.69E+33 n = -5.11 E = 29.69
234 Ai= 8.10E+11 ni= .50 Ei= 18.87
235 fcA = 0.4093 fctA = 275
236 fcb = 0.5907 fctb = 1226
237 fcc = 1.0 fctc = 5185 }
238 G25f: T-CH2 + CH -> C2H2 + H { A = 4.00E+13 n = .00 E = .00 }
239 G26f: T-CH2 + T-CH2 -> C2H2 + H2 { A = 1.60E+15 n = .00 E = 49.97 }
240 G27 : T-CH2 + T-CH2 -> C2H2 + 2 H { A = 2.00E+14 n = .00 E = 45.98 }
241
242
243 # Methylene (singlet)
244 # -------------------
245
246 G28f: S-CH2 + N2 -> T-CH2 + N2 { A = 1.50E+13 n = .00 E = 2.51 }
247 G29f: S-CH2 + AR -> T-CH2 + AR { A = 9.00E+12 n = .00 E = 2.51 }
248 G30f: S-CH2 + CO -> T-CH2 + CO { A = 9.00E+12 n = .00 E = .00 }
249 G31f: S-CH2 + CO2 -> T-CH2 + CO2 { A = 7.00E+12 n = .00 E = .00 }
250 G32f: S-CH2 + H2O -> T-CH2 + H2O { A = 3.00E+13 n = .00 E = .00 }
251
252 G33f: S-CH2 + H -> CH + H2 { A = 3.00E+13 n = .00 E = .00 }
253 G34f: S-CH2 + O -> CO + H2 { A = 1.50E+13 n = .00 E = .00 }
254 G35f: S-CH2 + O -> HCO + H { A = 1.50E+13 n = .00 E = .00 }
255 G36f: S-CH2 + H2 -> CH3 + H { A = 7.00E+13 n = .00 E = .00 }
256 G37 : S-CH2 + O2 -> CO + OH + H { A = 2.80E+13 n = .00 E = .00 }
257 G38f: S-CH2 + O2 -> CO + H2O { A = 1.20E+13 n = .00 E = .00 }
258 G39f: S-CH2 + H2O + M9 -> CH3OH + M9 { A = 1.88E+38 n = -6.36 E = 21.09
259 Ai= 4.82E+17 ni= -1.16 Ei= 4.79
260 fcA = 0.3973 fctA = 208
261 fcb = 0.6027 fctb = 3922
262 fcc = 1.0 fctc = 10180 }
263
264 G40f: S-CH2 + OH -> CH2O + H { A = 3.00E+13 n = .00 E = .00 }
265 G41 : S-CH2 + H2O -> CH2O + H2 { A = 6.82E+10 n = .25 E = -3.91 }
266 G42f: S-CH2 + CO2 -> CH2O + CO { A = 1.40E+13 n = .00 E = .00 }
267
268
269 # Formaldehyde
270 # ------------
271
272 # Dames & Golden 2013
273 G43f: CH2OH + M9 -> CH2O + H + M9 { A = 3.50E+21 n = -1.99 E = 100.41
274 Ai= 7.37E+10 ni= 0.81 Ei= 165.61
275 fcA = 0.156 fctA = 900
276 fcb = 0.844 fctb = 1
277 fcc = 1.0 fctc = 3315 }
278 G44f: CH3O + M9 -> CH2O + H + M9 { A = 6.02E+16 n = -0.55 E = 75.41
279 Ai= 1.13E+10 ni= 1.21 Ei= 100.77
280 fcA = 0.659 fctA = 28
281 fcb = 0.341 fctb = 1000
282 fcc = 1.0 fctc = 2339 }
283
284 G45f: CH2O + H -> HCO + H2 { A = 5.74E+07 n = 1.90 E = 11.47 }
285 G46f: CH2O + O -> HCO + OH { A = 3.90E+13 n = .00 E = 14.81 }
286 G47f: CH2O + OH -> HCO + H2O { A = 3.43E+09 n = 1.18 E = -1.87 }
287 G48f: CH2O + O2 -> HCO + HO2 { A = 1.00E+14 n = .00 E = 167.36 }
288 G49f: CH2O + HO2 -> HCO + H2O2 { A = 5.60E+06 n = 2.00 E = 50.21 }
289
290 G50f: CH2O + CH -> CH2CO + H { A = 9.46E+13 n = .00 E = -2.16 }
291
292
293 # Methyl radical
294 # --------------
295
296 # Golden 2013
297 # Baulch et al.; Troe Ushakov
298 G51f: CH3 + H + M9 -> CH4 + M9 { A = 2.79E+34 n = -5.10 E = 11.65
299 Ai= 4.36E+13 ni= 0.19 Ei= .00
300 fcA = 0.37 fctA = 61
301 fcb = 0.63 fctb = 3315
302 fcc = 1.0 fctc = 1e10 }
303
304 # Harding, Klippenstein, Georgievskii 2005
305 # Reactions lumped - Products changed
306 G52f: CH3 + O -> CH2O + H { A = 5.54E+13 n = 0.05 E = -0.57 }
307
308 G54f: CH3 + OH + M9 -> CH3OH + M9 { A = 4.00E+36 n = -5.92 E = 13.14
309 Ai= 2.79E+18 ni= -1.43 Ei= 5.57
310 fcA = 0.588 fctA = 195
311 fcb = 0.412 fctb = 5900
312 fcc = 1.0 fctc = 6394 }
313 G55f: CH3 + OH -> T-CH2 + H2O { A = 5.60E+07 n = 1.60 E = 22.68 }
314 G56f: CH3 + OH -> S-CH2 + H2O { A = 6.44E+17 n = -1.34 E = 5.93 }
315 G57: CH3 + OH -> CH2O + H2 { A = 8.00E+09 n = .00 E = -7.34 }
316
317 # Petersen et al. 2007
318 G58f: CH3 + O2 -> CH3O + O { A = 1.38E+13 n = .00 E = 127.70 }
319 G59f: CH3 + O2 -> CH2O + OH { A = 5.87E+11 n = .00 E = 57.91 }
320 G60f: CH3 + O2 + M0 -> CH3O2 + M0 { A = 3.82E+31 n = -4.89 E = 14.36
321 Ai= 1.01E+08 ni= 1.63 Ei= .00
322 fca = 0.955 fcta = 880.1
323 fcb = 0.045 fctb = 2.5E+9
324 fcc = 1 fctc = 1.786E+09 }
325 G61f: CH3O2 + CH3 -> CH3O + CH3O { A = 1.00E+13 n = .00 E = -5.02 }
326 G62 : CH3O2 + CH3O2 -> CH3O + CH3O + O2 { A = 1.40E+16 n = -1.61 E = 7.78 }
327 G63 : CH3O2 + HO2 -> CH3O + OH + O2 { A = 2.47E+11 n = .00 E = -6.57 }
328 G64 : CH3O2 + CH2O -> CH3O + OH + HCO { A = 1.99E+12 n = .00 E = 48.83 }
329
330 # Jasper, Klippensteion, Harding 2009
331 G65f: CH3 + HO2 -> CH3O + OH { A = 1.00E+12 n = 0.29 E = -2.87 }
332 G66f: CH3 + HO2 -> CH4 + O2 { A = 1.19E+05 n = 2.23 E = -12.65 }
333
334 G67f: CH3 + H2O2 -> CH4 + HO2 { A = 2.45E+04 n = 2.47 E = 21.67 }
335 G68f: CH3 + HCO -> CH4 + CO { A = 2.65E+13 n = .00 E = .00 }
336 G69f: CH3 + CH2O -> CH4 + HCO { A = 3.32E+03 n = 2.81 E = 24.52 }
337
338 G70f: CH3 + C -> C2H2 + H { A = 5.00E+13 n = .00 E = .00 }
339 G71f: CH3 + CH -> C2H3 + H { A = 3.00E+13 n = .00 E = .00 }
340 G72f: CH3 + T-CH2 -> C2H4 + H { A = 1.00E+14 n = .00 E = .00 }
341 G73f: CH3 + S-CH2 -> C2H4 + H { A = 1.20E+13 n = .00 E = -2.39 }
342 G74f: CH3 + CH3 -> C2H5 + H { A = 6.84E+12 n = 0.10 E = 44.35 }
343
344
345 # Methoxy radical
346 # ---------------
347
348 G75f: CH3O + H + M9 -> CH3OH + M9 { A = 4.66E+41 n = -7.44 E = 58.91
349 Ai= 2.43E+12 ni= .52 Ei= 0.21
350 fcA = 0.30 fctA = 100
351 fcb = 0.70 fctb = 90000
352 fcc = 1.0 fctc = 10000 }
353 G76f: CH3O + H -> CH3 + OH { A = 1.50E+12 n = 0.50 E = -0.46 }
354 G77f: CH3O + H -> S-CH2 + H2O { A = 2.62E+14 n = -0.23 E = 4.48 }
355
356 G78f: CH3O + H -> CH2O + H2 { A = 2.00E+13 n = .00 E = .00 }
357 G79f: CH3O + O -> CH2O + OH { A = 1.00E+13 n = .00 E = .00 }
358 G80f: CH3O + OH -> CH2O + H2O { A = 5.00E+12 n = .00 E = .00 }
359
360 # Baulch et al. 2005
361 G81f: CH3O + O2 -> CH2O + HO2 { A = 6.17E+10 n = .00 E = 7.32 }
362
363 G82f: CH2OH + H + M9 -> CH3OH + M9 { A = 4.36E+31 n = -4.65 E = 21.26
364 Ai= 1.06E+12 ni= 0.50 Ei= 0.36
365 fcA = 0.400 fctA = 100
366 fcb = 0.600 fctb = 9000
367 fcc = 1.0 fctc = 10000 }
368 G83f: CH2OH + H -> CH3 + OH { A = 1.65E+11 n = 0.65 E = -1.19 }
369 G84f: CH2OH + H -> S-CH2 + H2O { A = 3.28E+13 n = -0.09 E = 2.55 }
370
371 G85f: CH2OH + H -> CH2O + H2 { A = 2.00E+13 n = .00 E = .00 }
372 G86f: CH2OH + O -> CH2O + OH { A = 1.00E+13 n = .00 E = .00 }
373 G87f: CH2OH + OH -> CH2O + H2O { A = 5.00E+12 n = .00 E = .00 }
374 G88f: CH2OH + O2 -> CH2O + HO2 { A = 1.80E+13 n = .00 E = 3.77 }
375
376 G89f: CH3O + H -> CH2OH + H { A = 4.15E+07 n = 1.63 E = 8.05 }
377
378
379 # Methane
380 # -------
381
382 G90f: CH4 + H -> CH3 + H2 { A = 6.60E+08 n = 1.62 E = 45.36 }
383 G91f: CH4 + O -> CH3 + OH { A = 1.02E+09 n = 1.50 E = 35.98 }
384 G92f: CH4 + OH -> CH3 + H2O { A = 1.00E+08 n = 1.60 E = 13.05 }
385 G94f: CH4 + T-CH2 -> CH3 + CH3 { A = 2.46E+06 n = 2.00 E = 34.60 }
386 G95f: CH4 + S-CH2 -> CH3 + CH3 { A = 1.60E+13 n = .00 E = -2.39 }
387
388 G93f: CH4 + CH -> C2H4 + H { A = 6.00E+13 n = .00 E = .00 }
389
390
391 # Methanol
392 # --------
393
394 G96f: CH3OH + H -> CH2OH + H2 { A = 1.70E+07 n = 2.10 E = 20.38 }
395 G97f: CH3OH + O -> CH2OH + OH { A = 3.88E+05 n = 2.50 E = 12.97 }
396 G98f: CH3OH + OH -> CH2OH + H2O { A = 1.44E+06 n = 2.00 E = -3.52 }
397 G99f: CH3OH + CH3 -> CH2OH + CH4 { A = 3.00E+07 n = 1.50 E = 41.59 }
398
399 G100f: CH3OH + H -> CH3O + H2 { A = 4.20E+06 n = 2.10 E = 20.38 }
400 G101f: CH3OH + O -> CH3O + OH { A = 1.30E+05 n = 2.50 E = 20.92 }
401 G102f: CH3OH + OH -> CH3O + H2O { A = 6.30E+06 n = 2.00 E = 6.28 }
402 G103f: CH3OH + CH3 -> CH3O + CH4 { A = 1.00E+07 n = 1.50 E = 41.59 }
403
404
405 # Acetyl radical
406 # --------------
407
408 G104f: C2H + H + M9 -> C2H2 + M9 { A = 2.60E+33 n = -4.80 E = 7.95
409 Ai= 1.00E+17 ni= -1.00 Ei= .00
410 fcA = 0.3536 fctA = 132
411 fcb = 0.6464 fctb = 1315
412 fcc = 1.0 fctc = 5566 }
413 G105f: C2H + O -> CH + CO { A = 5.00E+13 n = .00 E = .00 }
414 G106f: C2H + OH -> HCCO + H { A = 2.00E+13 n = .00 E = .00 }
415 G107f: C2H + O2 -> HCO + CO { A = 1.00E+13 n = .00 E = -3.16 }
416
417 # Carl, Vereecken & Peeters 2007
418 G108f: C2H + H2 -> C2H2 + H { A = 2.36E+05 n = 2.57 E = 1.08 }
419
420
421 # Ketenyl radical
422 # ---------------
423 # Revised based on Carl, Vereecken & Peeters 2007
424
425 G109f: HCCO + H -> S-CH2 + CO { A = 1.00E+14 n = .00 E = .00 }
426 G110f: HCCO + CH -> C2H2 + CO { A = 5.00E+13 n = .00 E = .00 }
427 G111f: HCCO + T-CH2 -> C2H3 + CO { A = 3.00E+13 n = .00 E = .00 }
428 G112f: HCCO + CH3 -> C2H4 + CO { A = 5.00E+13 n = .00 E = .00 }
429 G113 : HCCO + HCCO -> C2H2 + 2 CO { A = 1.00E+13 n = .00 E = .00 }
430
431 G114 : HCCO + O -> H + 2 CO { A = 7.22E+13 n = .00 E = .00 }
432
433 # Mai, Raghunath, Le, Huynh, Nam, Lin 2014
434 G115f: HCCO + OH -> CH2O + CO { A = 1.88E+16 n = -0.59 E = 0.61 }
435 G116f: HCCO + OH -> T-CH2 + CO2 { A = 8.97E+04 n = 2.09 E = -9.19 }
436
437 # Klippenstein, Miller, Harding 2002
438 G117 : HCCO + O2 -> CO2 + CO + H { A = 4.78E+12 n = -0.14 E = 4.81 }
439 G118 : HCCO + O2 -> 2CO + OH { A = 1.91E+11 n = -0.02 E = 4.28 }
440
441
442 # Acetylene
443 # ---------
444
445 # Miller & Klippenstein 2004
446 # Refitted TROE form
447 G119f: C2H2 + H + M9 -> C2H3 + M9 { A = 6.34E+31 n = -4.66 E = 15.82
448 Ai= 1.71E+10 ni= 1.27 Ei= 11.33
449 fcA = 0.751 fctA = 12.1
450 fcb = 0.249 fctb = 10000
451 fcc = 1.0 fctc = 5493 }
452
453 # Nguyen, Vereecken, Peeters 2006 - Total rate
454 # Rajak & Maiti 2010 - Branching ratios
455 G120f: C2H2 + O -> HCCO + H { A = 2.96E+09 n = 1.28 E = 10.34 }
456 G121f: C2H2 + O -> T-CH2 + CO { A = 7.40E+08 n = 1.28 E = 10.34 }
457
458 # Tsang & Hampson 1986
459 # Modified for Collision Limit
460 G122f: C2H + OH -> C2H2 + O { A = 1.81E+13 n = .00 E = .00 }
461
462 # Senosiain, Klippenstein & Miller 2005
463 # HCCOH lumped into CH2CO
464 G123f: C2H2 + OH -> C2H + H2O { A = 2.63E+06 n = 2.14 E = 71.38 }
465 G124f: C2H2 + OH -> CH2CO + H { A = 2.10E+01 n = 3.22 E = -1.76 }
466 G125f: C2H2 + OH -> CH3 + CO { A = 1.28E+09 n = 0.73 E = 10.79 }
467
468 # Laskin & Wang 1999
469 G126f: C2H2 + M9 -> H2C2 + M9 { A = 2.45E+15 n = -0.64 E = 207.94 }
470 G127f: H2C2 + O2 -> 2 HCO { A = 1.00E+13 n = .00 E = .00 }
471
472
473 # Ketene
474 # ------
475 # Updated by Eiteneer & Frenklach 2003
476
477 G128f: CH2CO + H -> HCCO + H2 { A = 5.00E+13 n = .00 E = 33.47 }
478 G129f: CH2CO + O -> HCCO + OH { A = 1.00E+13 n = .00 E = 33.47 }
479 G130f: CH2CO + OH -> HCCO + H2O { A = 7.50E+12 n = .00 E = 8.37 }
480 G131f: CH2CO + T-CH2 -> HCCO + CH3 { A = 3.60E+13 n = .00 E = 46.02 }
481
482 # Woods & Haynes 1994
483 G132f: CH2CO + CH3 -> HCCO + CH4 { A = 7.50E+12 n = .00 E = 54.39 }
484 G133f: CH2CO + CH3 -> C2H5 + CO { A = 9.00E+10 n = .00 E = .00 }
485
486 # Senosiain, Klippenstein & Miller 2006
487 G134f: CH2CO + H -> CH3 + CO { A = 7.77E+08 n = 1.45 E = 11.63 }
488
489 # Lee & Bozzelli 2002
490 G135f: CH2CO + OH -> CH2OH + CO { A = 5.00E+12 n = .00 E = .00 }
491 G136f: CH2CO + T-CH2 -> C2H4 + CO { A = 1.00E+12 n = .00 E = .00 }
492
493 G137f: CH2CO + O -> T-CH2 + CO2 { A = 1.75E+12 n = .00 E = 5.65 }
494
495
496 # Vinyl radical
497 # -------------
498
499 G138f: C2H3 + H + M9 -> C2H4 + M9 { A = 1.40E+30 n = -3.86 E = 13.89
500 Ai= 6.08E+12 ni= 0.27 Ei= 1.17
501 fcA = 0.218 fctA = 207.5
502 fcb = 0.782 fctb = 2663
503 fcc = 1.0 fctc = 6095 }
504 G139f: C2H3 + H -> C2H2 + H2 { A = 3.00E+13 n = .00 E = .00 }
505
506 # Harding, Klippenstein & Georgievskii 2005
507 G140f: C2H3 + O -> CH2CHO { A = 1.03E+13 n = 0.21 E = -1.79 }
508
509 G141f: C2H3 + OH -> C2H2 + H2O { A = 5.00E+12 n = .00 E = .00 }
510 G142f: C2H3 + O2 -> C2H2 + HO2 { A = 1.34E+06 n = 1.61 E = -1.61 }
511
512 # Stoliarov et al. 2002
513 G143f: C2H3 + CH3 -> C2H2 + CH4 { A = 9.03E+12 n = .00 E = -3.20 }
514
515 G144f: C2H3 + O2 -> CH2CHO + O { A = 3.03E+11 n = 0.29 E = 0.05 }
516 G145f: C2H3 + O2 -> HCO + CH2O { A = 4.58E+16 n = -1.39 E = 4.25 }
517
518 G146f: C2H3 + H2O2 -> C2H4 + HO2 { A = 1.21E+10 n = .00 E = -2.49 }
519 G147f: C2H3 + HCO -> C2H4 + CO { A = 9.00E+13 n = .00 E = .00 }
520
521
522 # CH2CHO
523 # ------
524
525 # Senosiain, Klippenstein & Miller 2006
526 G148f: CH2CHO -> CH2CO + H { A = 1.32E+34 n = -6.57 E = 202.45 }
527 G149f: CH2CHO -> CH3 + CO { A = 6.51E+34 n = -6.87 E = 197.46 }
528
529 # Same as for C2H5 + O
530 G150f: CH2CHO + O -> CH2O + HCO { A = 3.17E+13 n = 0.03 E = -1.65 }
531
532 G151 : CH2CHO + O2 -> CH2O + CO + OH { A = 1.81E+10 n = .00 E = 0.00 }
533 G152 : CH2CHO + O2 -> 2 HCO + OH { A = 2.35E+10 n = .00 E = 0.00 }
534 G153f: CH2CHO + H -> CH2CO + H2 { A = 1.10E+13 n = .00 E = 0.00 }
535 G154f: CH2CHO + OH -> CH2CO + H2O { A = 1.20E+13 n = .00 E = 0.00 }
536
537 G155f: CH2CHO + H -> CH3 + HCO { A = 2.20E+13 n = .00 E = 0.00 }
538 G156f: CH2CHO + OH -> CH2OH + HCO { A = 3.01E+13 n = .00 E = 0.00 }
539 G157f: CH2CHO + CH3 -> C2H5 + HCO { A = 4.90E+14 n = -0.50 E = .00 }
540
541
542 # Acetaldehyde
543 # ------------
544
545 # Baulch et al. 2005 - HPL - Backward
546 # Modified for collision limit
547 G158f: CH3 + HCO -> CH3CHO { A = 5.00E+13 n = .00 E = .00 }
548
549 G159f: CH3CHO + O -> CH2CHO + OH { A = 2.92E+12 n = .00 E = 7.57 }
550 G160f: CH3CHO + H -> CH2CHO + H2 { A = 2.05E+09 n = 1.16 E = 10.06 }
551
552 G161 : CH3CHO + H -> CH3 + CO + H2 { A = 2.05E+09 n = 1.16 E = 10.06 }
553 G162 : CH3CHO + O -> CH3 + CO + OH { A = 2.92E+12 n = .00 E = 7.57 }
554 G163 : CH3CHO + OH -> CH3 + CO + H2O { A = 2.34E+10 n = .73 E = -4.66 }
555 G164 : CH3CHO + O2 -> CH3 + CO + HO2 { A = 3.01E+13 n = .00 E = 163.80 }
556 G165 : CH3CHO + HO2 -> CH3 + CO + H2O2 { A = 3.01E+12 n = .00 E = 49.89 }
557 G166 : CH3CHO + CH3 -> CH3 + CO + CH4 { A = 2.72E+06 n = 1.77 E = 24.77 }
558
559
560 # Ethylene
561 # --------
562
563 # Pilla, Davidson, Hanson 2010
564 G167f: C2H4 + M9 -> H2C2 + H2 + M9 { A = 5.50E+14 n = .00 E = 226.97 }
565
566 # Miller & Klippenstein 2004
567 # Refitted TROE form
568 G168f: C2H4 + H + M9 -> C2H5 + M9 { A = 2.03E+39 n = -6.64 E = 24.14
569 Ai= 1.37E+09 ni= 1.46 Ei= 5.67
570 fcA = 0.74 fctA = 361.7
571 fcb = 0.26 fctb = 10000
572 fcc = 1.0 fctc = 9096 }
573
574 # Huynh, Panasewicz, Ratkiewicz, Truong 2007
575 # Closer to the recommendation of Baulch et al. 2005
576 G169f: C2H4 + H -> C2H3 + H2 { A = 1.27E+05 n = 2.75 E = 48.74 }
577
578 # Nguyen, Vereecken, Hou, Nguyen, Peeters 2005
579 G170f: C2H4 + O -> CH2CHO + H { A = 7.66E+09 n = 0.88 E = 4.77 }
580 G171f: C2H4 + O -> T-CH2 + CH2O { A = 7.15E+04 n = 2.47 E = 3.89 }
581 G172f: C2H4 + O -> CH3 + HCO { A = 3.89E+08 n = 1.36 E = 3.71 }
582
583 # Vasu, Hong, Davidson, Hanson, Golden 2010
584 G173f: C2H4 + OH -> C2H3 + H2O { A = 2.23E+04 n = 2.75 E = 9.27 }
585
586 # Wang 2001
587 G174f: C2H4 + O2 -> C2H3 + HO2 { A = 4.22E+13 n = .00 E = 259.83 }
588 G175 : C2H4 + O2 -> CH3 + CO2 + H { A = 4.90E+12 n = 0.42 E = 317.15 }
589
590 # Miller & Klippenstein 2013
591 G176f: C2H4 + CH3 -> C2H3 + CH4 { A = 2.06E-01 n = 3.94 E = 51.98 }
592
593 G177f: C2H4 + CH3 + M9 -> N-C3H7 + M9 { A = 3.00E+63 n = -14.6 E = 76.02
594 Ai= 2.55E+06 ni= 1.60 Ei= 23.85
595 fcA = 0.8106 fctA = 277
596 fcb = 0.1894 fctb = 8748
597 fcc = 1.0 fctc = 7891 }
598
599
600 # Ethyl radical
601 # -------------
602
603 G178f: C2H5 + H + M9 -> C2H6 + M9 { A = 1.99E+41 n = -7.08 E = 27.97
604 Ai= 5.21E+17 ni= -0.99 Ei= 6.61
605 fcA = 0.1578 fctA = 125
606 fcb = 0.8422 fctb = 2219
607 fcc = 1.0 fctc = 6882 }
608
609 G179f: C2H5 + H -> C2H4 + H2 { A = 2.00E+12 n = .00 E = .00 }
610
611 # Miller, Klippenstein & Robertson 2000
612 G180f: C2H5 + O2 -> C2H4 + HO2 { A = 1.92E+07 n = 1.02 E = -8.51 }
613
614 # Zhu, Xu & Lin 2004
615 G181f: C2H5 + CH3 -> C2H4 + CH4 { A = 1.18E+04 n = 2.45 E = 12.22 }
616
617 # Harding, Klippenstein & Georgievskii 2005
618 G182f: C2H5 + O -> CH3 + CH2O { A = 3.17E+13 n = 0.03 E = -1.65 }
619
620 # Ludwig et al. 2006
621 G183f: C2H5 + HO2 -> C2H5O + OH { A = 3.10E+13 n = .00 E = .00 }
622
623 G184f: C2H5 + HCO -> C2H6 + CO { A = 1.20E+14 n = .00 E = .00 }
624 G185f: C2H5 + HO2 -> C2H6 + O2 { A = 3.00E+11 n = .00 E = .00 }
625 G186f: C2H5 + HO2 -> C2H4 + H2O2 { A = 3.00E+11 n = .00 E = .00 }
626
627
628 # Ethoxy radical
629 # --------------
630
631 # Dames 2014
632 G187f: C2H5O + M9 -> CH3 + CH2O + M9 { A = 4.70E+25 n = -3.00 E = 69.17
633 Ai= 6.31E+10 ni= 0.93 Ei= 71.54
634 fcA = 0.574 fctA = 0.3
635 fcb = 0.426 fctb = 2046
636 fcc = 1.0 fctc = 1e5 }
637
638 # Baulch et al. 2005
639 G188f: C2H5O + O2 -> CH3CHO + HO2 { A = 2.29E+10 n = .00 E = 3.66 }
640
641
642 # Ethane
643 # ------
644
645 # Oehlschlaeger et al. 2005
646 G189f: C2H6 + M9 -> 2 CH3 + M9 { A = 3.72E+65 n =-13.14 E = 425.01
647 Ai= 1.88E+50 ni= -9.72 Ei= 449.12
648 fcA = 0.61 fctA = 100
649 fcb = 0.39 fctb = 1900
650 fcc = 1.0 fctc = 6000 }
651
652 # Chakraborty, Zhao, Lin, & Truhlar 2006
653 # Fit 500-2000K
654 G190f: C2H6 + H -> C2H5 + H2 { A = 1.70E+05 n = 2.70 E = 24.02 }
655
656 # Huynh, Zhang, Truong 2008
657 G191f: C2H6 + O -> C2H5 + OH { A = 3.17E+01 n = 3.80 E = 13.10 }
658
659 # Krasnoperov & Michael 2004
660 G192f: C2H6 + OH -> C2H5 + H2O { A = 1.61E+06 n = 2.22 E = 3.10 }
661
662 # Carstensen & Dean 2005
663 G193f: C2H6 + HO2 -> C2H5 + H2O2 { A = 2.61E+02 n = 3.37 E = 66.58 }
664
665 G194f: C2H6 + S-CH2 -> C2H5 + CH3 { A = 4.00E+13 n = .00 E = -2.30 }
666
667 # Peukert, Labbe, Sivaramakrishnan, Michael 2013
668 G195f: C2H6 + CH3 -> C2H5 + CH4 { A = 3.45E+01 n = 3.44 E = 43.47 }
669
670
671 # Propyl radicals
672 # ---------------
673
674
675 # Curran 2006 - HPL
676 G196f: C3H6 + H + M9 -> N-C3H7 + M9 { A = 6.26E+38 n = -6.66 E = 29.29
677 Ai= 2.50E+11 ni= 0.51 Ei= 10.96
678 fcA = 0.0 fctA = 1000
679 fcb = 1.0 fctb = 1310
680 fcc = 1.0 fctc = 48097 }
681 G197f: C3H6 + H + M9 -> I-C3H7 + M9 { A = 8.70E+42 n = -7.50 E = 19.75
682 Ai= 4.24E+11 ni= 0.51 Ei= 5.15
683 fcA = 0.0 fctA = 1000
684 fcb = 1.0 fctb = 645.4
685 fcc = 1.0 fctc = 6844.3 }
686
687 G198f: N-C3H7 + H -> C2H5 + CH3 { A = 3.70E+24 n = -2.92 E = 52.32 }
688 G199f: I-C3H7 + H -> C2H5 + CH3 { A = 1.40E+28 n = -3.94 E = 66.59 }
689 G200f: N-C3H7 + H -> C3H6 + H2 { A = 1.80E+12 n = .00 E = .00 }
690 G201f: I-C3H7 + H -> C3H6 + H2 { A = 3.20E+12 n = .00 E = .00 }
691 G202f: N-C3H7 + O -> C2H5 + CH2O { A = 9.60E+13 n = .00 E = .00 }
692 G203f: I-C3H7 + O -> CH3CHO + CH3 { A = 9.60E+13 n = .00 E = .00 }
693 G204f: N-C3H7 + OH -> C3H6 + H2O { A = 2.41E+13 n = .00 E = .00 }
694 G205f: I-C3H7 + OH -> C3H6 + H2O { A = 2.41E+13 n = .00 E = .00 }
695
696 # DeSain, Miller, Klippenstein & Taatjes 2003
697 G206f: N-C3H7 + O2 -> C3H6 + HO2 { A = 3.70E+16 n = -1.63 E = 14.30 }
698 G207f: I-C3H7 + O2 -> C3H6 + HO2 { A = 6.70E+20 n = -3.02 E = 10.48 }
699
700 # Knyazev & Slagle 2001 - Total rate
701 # Shafir, Slagle & Knyazev 2003 - Branching ratio
702 G208f: N-C3H7 + CH3 -> C3H6 + CH4 { A = 3.31E+12 n = .00 E = -3.22 }
703
704
705 # Propane
706 # -------
707
708 # From Tsang 1988
709 G209f: N-C3H7 + H + M9 -> C3H8 + M9 { A = 4.42E+61 n =-13.55 E = 47.52
710 Ai= 3.61E+13 ni= .00 Ei= .00
711 fcA = 0.685 fctA = 369
712 fcb = 0.315 fctb = 3285
713 fcc = 1.0 fctc = 6667 }
714 G210f: I-C3H7 + H + M9 -> C3H8 + M9 { A = 1.70E+58 n =-12.08 E = 47.13
715 Ai= 2.40E+13 ni= .00 Ei= .00
716 fcA = 0.502 fctA = 1314
717 fcb = 0.498 fctb = 1314
718 fcc = 1.0 fctc = 50000 }
719
720 # Oehlschlaeger et al. 2005
721 G211f: C3H8 + M9 -> C2H5 + CH3 + M9 { A = 5.64E+74 n =-15.74 E = 413.04
722 Ai= 1.29E+37 ni= -5.84 Ei= 407.47
723 fcA = 0.69 fctA = 50
724 fcb = 0.31 fctb = 3000
725 fcc = 1.0 fctc = 9000 }
726 # Carstensen & Dean 2009
727 G212f: C3H8 + H -> N-C3H7 + H2 { A = 9.36E+07 n = 1.97 E = 34.31 }
728 G213f: C3H8 + H -> I-C3H7 + H2 { A = 7.60E+07 n = 1.86 E = 23.43 }
729
730 G214f: C3H8 + O -> N-C3H7 + OH { A = 1.90E+05 n = 2.68 E = 15.55 }
731 G215f: C3H8 + O -> I-C3H7 + OH { A = 4.76E+04 n = 2.71 E = 08.81 }
732
733 # Sivaramkrishnan, Srinivasan, Su, Michael 2009
734 G216f: C3H8 + OH -> N-C3H7 + H2O { A = 5.15E+03 n = 2.94 E = -1.75 }
735 G217f: C3H8 + OH -> I-C3H7 + H2O { A = 1.81E+05 n = 2.44 E = -2.24 }
736
737 G218f: C3H8 + CH3 -> N-C3H7 + CH4 { A = 9.03E-01 n = 3.65 E = 29.93 }
738 G219f: C3H8 + CH3 -> I-C3H7 + CH4 { A = 1.51E+00 n = 3.46 E = 29.93 }
739 G220f: C3H8 + HO2 -> N-C3H7 + H2O2 { A = 4.76E+04 n = 2.55 E = 69.00 }
740 G221f: C3H8 + HO2 -> I-C3H7 + H2O2 { A = 9.63E+03 n = 2.60 E = 58.20 }
741
742
743
744 #=========================================================================#
745 # #
746 # "Experimental and Modeling Study of Shock-Tube Oxidation of Acetylene" #
747 # B. Eiteneer and M. Frenklach #
748 # Int. J. Chem. Kinet. 35, 391:414 (2003) #
749 # #
750 #=========================================================================#
751
752
753 # Propynylidene
754 # -------------
755
756 R005f: C3H2 + O -> C3H2O { A = 1.36E+14 n = .00 E = .00 }
757 R006f: C3H2 + OH -> C2H2 + HCO { A = 1.00E+13 n = .00 E = .00 }
758 R007f: C3H2 + O2 -> HCCO + CO + H { A = 1.25E+11 n = .00 E = 4.18 }
759 R008f: C3H2 + CH -> C4H2 + H { A = 5.00E+13 n = .00 E = .00 }
760 R009f: C3H2 + T-CH2 -> N-C4H3 + H { A = 5.00E+13 n = .00 E = .00 }
761 R010f: C3H2 + CH3 -> C4H4 + H { A = 5.00E+12 n = .00 E = .00 }
762 R011f: C3H2 + HCCO -> N-C4H3 + CO { A = 1.00E+13 n = .00 E = .00 }
763
764
765 # Propynal
766 # --------
767
768 # Estimated
769 R012f: C2H + HCO -> C3H2O { A = 5.00E+13 n = .00 E = .00 }
770 # From P-C3H4 + H
771 R013f: C3H2O + H -> C2H2 + HCO { A = 3.46E+12 n = 0.44 E = 22.86 }
772
773 # Taken from CH3CHO
774 R014 : C3H2O + H -> C2H + CO + H2 { A = 2.05E+09 n = 1.16 E = 10.06 }
775 R015 : C3H2O + O -> C2H + CO + OH { A = 2.92E+12 n = .00 E = 7.57 }
776 R016 : C3H2O + O2 -> C2H + CO + HO2 { A = 3.01E+13 n = .00 E = 163.80 }
777 R017 : C3H2O + OH -> C2H + CO + H2O { A = 2.34E+10 n = .73 E = -4.66 }
778 R018 : C3H2O + HO2 -> C2H + CO + H2O2 { A = 3.01E+12 n = .00 E = 49.89 }
779 R019 : C3H2O + CH3 -> C2H + CO + CH4 { A = 2.72E+06 n = 1.77 E = 24.77 }
780
781
782 # Propargyl radical
783 # -----------------
784
785 R020f: C2H2 + HCCO -> C3H3 + CO { A = 1.00E+11 n = .00 E = 12.55 }
786
787 # Tsang & Hampson 1986
788 R021f: C2H + CH3 -> C3H3 + H { A = 2.41E+13 n = .00 E = .00 }
789
790 # Polino, Klippenstein, Harding, Georgievskii 2013
791 R022f: C2H2 + S-CH2 -> C3H3 + H { A = 3.97E+15 n = -0.57 E = -0.02 }
792
793 # 2x rate for C2H3+H
794 R023f: C3H2 + H + M9 -> C3H3 + M9 { A = 2.80E+30 n = -3.86 E = 13.89
795 Ai= 1.02E+13 ni= .27 Ei= 1.17
796 fcA = 0.218 fctA = 207.5
797 fcb = 0.782 fctb = 2663
798 fcc = 1.0 fctc = 6095 }
799
800 # Miller & Klippenstein 2003 (1bar)
801 R024f: C3H3 + H -> C3H2 + H2 { A = 1.10E+10 n = 1.13 E = 58.28 }
802
803 # Adapted from C2H2 + OH
804 R025f: C3H3 + OH -> C2H3CHO { A = 2.10E+01 n = 3.22 E = -1.76 }
805 R026f: C3H3 + OH -> C2H4 + CO { A = 1.28E+09 n = 0.73 E = 10.79 }
806
807 # 1/2 rate for C2H4+OH
808 R027f: C3H3 + OH -> C3H2 + H2O { A = 1.13E+05 n = 2.28 E = 10.32 }
809
810 # Lee, Nam & Choi 2006
811 # Kwon, Nam, Youn, Joo, Lee, & Choi 2006
812 # Slagle, Gmurczyk, Batt & Gutman 1991
813 R029f: C3H3 + O -> C3H2O + H { A = 1.38E+14 n = .00 E = .00 }
814
815 # Hahn, Klippenstein, Miller 2001
816 R030f: C3H3 + O2 -> CH2CO + HCO { A = 1.70E+05 n = 1.70 E = 6.28 }
817
818 R031 : C3H3 + HO2 -> C2H3 + CO + OH { A = 8.00E+11 n = .00 E = .00 }
819
820 # Wang 2001
821 R032f: C3H3 + HO2 -> A-C3H4 + O2 { A = 3.00E+11 n = .00 E = .00 }
822 R033f: C3H3 + HO2 -> P-C3H4 + O2 { A = 3.00E+11 n = .00 E = .00 }
823 R034f: P-C3H4 + O2 -> CH3 + HCO + CO { A = 4.00E+14 n = .00 E = 175.43 }
824
825 R035f: C3H3 + HCO -> A-C3H4 + CO { A = 2.50E+13 n = .00 E = .00 }
826 R036f: C3H3 + HCO -> P-C3H4 + CO { A = 2.50E+13 n = .00 E = .00 }
827 R037f: C3H3 + CH -> I-C4H3 + H { A = 5.00E+13 n = .00 E = .00 }
828
829 # Miller, Melius 1992
830 R038f: C3H3 + T-CH2 -> C4H4 + H { A = 5.00E+13 n = .00 E = .00 }
831
832
833 # Propyne & Allene
834 # ----------------
835
836 # Thiesemann, Clifford, Taatjes, Klippenstein 2001
837 # Zhang, Maksyutenko, Kaiser 2012
838 R200f: C2H4 + CH -> A-C3H4 + H { A = 9.98E+14 n = -0.31 E = .00 }
839
840 # Miller & Klippenstein 2003 (1bar)
841 R039f: A-C3H4 -> P-C3H4 { A = 7.76E+39 n = -7.80 E = 328.22 }
842
843 # Giri, Fernandes, Bentz, Hippler, Olzmann 2011
844 R040f: P-C3H4 + M0 -> C3H3 + H + M0 { A = 2.15E+43 n = -6.81 E = 420.61 }
845 R041f: A-C3H4 + M0 -> C3H3 + H + M0 { A = 2.15E+43 n = -6.81 E = 420.61 }
846
847 # Miller, Senosiain, Klippenstein, Georgievskii 2008
848 # Refitted 800K-2500K - 1bar
849 R042f: A-C3H4 + H -> C2H2 + CH3 { A = 8.95E+13 n = -0.02 E = 47.07 }
850
851 # Sheen, Rosado-Reyes, Tsang 2013
852 R043f: C2H2 + CH3 -> P-C3H4 + H { A = 1.48E+11 n = 0.60 E = 59.86 }
853 R044f: P-C3H4 + H -> A-C3H4 + H { A = 1.58E+18 n = -1.00 E = 50.72 }
854
855 # Miller, Senosiain, Klippenstein, Georgievskii 2008
856 # P=1bar
857 R045f: A-C3H4 + H -> A-C3H5 { A = 2.01E+49 n =-10.77 E = 82.10 }
858 R046f: A-C3H4 + H -> T-C3H5 { A = 6.70E+42 n =-12.46 E = 68.45 }
859 R047f: P-C3H4 + H -> T-C3H5 { A = 8.83E+52 n =-12.36 E = 68.81 }
860 R048f: P-C3H4 + H -> S-C3H5 { A = 1.53E+49 n =-11.97 E = 59.18 }
861
862 # 1/2 the rate for C2H6
863 R049f: P-C3H4 + H -> C3H3 + H2 { A = 8.50E+04 n = 2.70 E = 24.02 }
864 R050f: P-C3H4 + O -> C3H3 + OH { A = 1.59E+01 n = 3.80 E = 13.10 }
865 R051f: P-C3H4 + OH -> C3H3 + H2O { A = 8.05E+05 n = 2.22 E = 3.10 }
866 R052f: P-C3H4 + CH3 -> C3H3 + CH4 { A = 1.73E+01 n = 3.44 E = 43.47 }
867 R053f: P-C3H4 + HO2 -> C3H3 + H2O2 { A = 1.30E+02 n = 3.37 E = 66.58 }
868
869 # Same as for C2H4
870 R054f: A-C3H4 + H -> C3H3 + H2 { A = 1.33E+06 n = 2.53 E = 51.21 }
871 R055f: A-C3H4 + OH -> C3H3 + H2O { A = 1.31E-01 n = 4.20 E = -3.60 }
872 R056f: A-C3H4 + CH3 -> C3H3 + CH4 { A = 2.27E+05 n = 2.00 E = 38.49 }
873 R057f: A-C3H4 + HO2 -> C3H3 + H2O2 { A = 9.76E+10 n = 0.12 E = 97.78 }
874
875 # Nguyen, Peeters & Vereecken 2006
876 # Total rate assigned
877 R058f: A-C3H4 + O -> CH2CO + T-CH2 { A = 9.63E+06 n = 2.05 E = 0.75 }
878
879 # Adapted from C2H2+O
880 # Zhao, Wu, Zhao et al. 2009 - Products
881 R059f: P-C3H4 + O -> C2H4 + CO { A = 3.70E+09 n = 1.28 E = 10.34 }
882
883 # From C2H2 + OH
884 R060f: P-C3H4 + OH -> CH2CO + CH3 { A = 2.10E+01 n = 3.22 E = -1.76 }
885 R061f: P-C3H4 + OH -> C2H5 + CO { A = 1.28E+09 n = 0.73 E = 10.79 }
886
887 R062f: A-C3H4 + C2H -> C2H2 + C3H3 { A = 1.00E+13 n = .00 E = .00 }
888 R063f: P-C3H4 + C2H -> C2H2 + C3H3 { A = 1.00E+13 n = .00 E = .00 }
889
890 # Liu, Maluc, Jonah 1988
891 R064f: A-C3H4 + OH -> CH2CO + CH3 { A = 4.03E+12 n = .00 E = -0.83 }
892
893
894 # Propenal
895 # --------
896
897 R065f: C2H3 + HCO -> C2H3CHO { A = 1.80E+13 n = .00 E = .00 }
898
899 # Baulch et al. 2005 - adapted from CH3CHO
900 R066 : C2H3CHO + H -> C2H3 + CO + H2 { A = 4.09E+09 n = 1.16 E = 10.06 }
901 R067 : C2H3CHO + O -> C2H3 + CO + OH { A = 5.84E+12 n = .00 E = 7.57 }
902 R068 : C2H3CHO + OH -> C2H3 + CO + H2O { A = 2.89E+08 n = 1.35 E = -6.58 }
903 R069 : C2H3CHO + HO2 -> C2H3 + CO + H2O2 { A = 4.09E+04 n = 2.50 E = 42.69 }
904 R070 : C2H3CHO + CH3 -> C2H3 + CO + CH4 { A = 3.49E-08 n = 6.21 E = 6.82 }
905
906
907 # Allyl radicals
908 # --------------
909
910 # Miller, Senosiain, Klippenstein, Georgievskii 2008
911 # Refitted 800K-2500K - P=1bar
912 R071f: C2H2 + CH3 -> S-C3H5 { A = 7.45E+43 n =-10.13 E = 77.50 }
913
914 # Davis, Law, Wang 1999 (1bar)
915 R072f: A-C3H5 -> T-C3H5 { A = 7.06E+56 n =-14.08 E = 317.43 }
916 R073f: A-C3H5 -> S-C3H5 { A = 5.00E+51 n =-13.02 E = 306.69 }
917 R074f: T-C3H5 -> S-C3H5 { A = 1.50E+48 n =-12.71 E = 225.52 }
918
919 # Klippenstein, Harding, Georgievskii, Miller 2008
920 # Fitted 400K-2500K
921 R075f: A-C3H5 + H -> A-C3H4 + H2 { A = 9.56E+03 n = 2.80 E = 13.77 }
922
923 # Tsang 1991
924 R076f: A-C3H5 + OH -> A-C3H4 + H2O { A = 6.03E+12 n = .00 E = .00 }
925 R077f: A-C3H5 + CH3 -> A-C3H4 + CH4 { A = 3.01E+12 n = -0.32 E = -0.55 }
926 R078f: A-C3H5 + C2H3 -> A-C3H4 + C2H4 { A = 2.41E+12 n = .00 E = .00 }
927 R079f: A-C3H5 + C2H5 -> A-C3H4 + C2H6 { A = 9.64E+11 n = .00 E = -0.55 }
928
929 # Lee & Bozzelli 2005
930 R081f: A-C3H5 + O2 -> A-C3H4 + HO2 { A = 2.06E+04 n = 2.19 E = 73.60 }
931 R082f: A-C3H5 + O2 -> C2H3CHO + OH { A = 3.36E+05 n = 1.81 E = 80.29 }
932 R083 : A-C3H5 + O2 -> C2H2 + CH2O + OH { A = 9.71E+20 n = -2.70 E = 104.52 }
933 R084f: A-C3H5 + O2 -> CH2CHO + CH2O { A = 3.08E+09 n = 0.37 E = 70.75 }
934
935 # Estimated from C2H5+O
936 # Park, lee, Choi 2003 - Products
937 R085f: A-C3H5 + O -> C2H3CHO + H { A = 3.17E+13 n = 0.03 E = -1.65 }
938
939 R086 : A-C3H5 + OH -> C2H3CHO + H2 { A = 4.20E+32 n = -5.16 E = 126.05 }
940 R087f: A-C3H5 + HCO -> C3H6 + CO { A = 6.00E+13 n = .00 E = .00 }
941 R088f: A-C3H5 + HO2 -> C3H6 + O2 { A = 2.66E+12 n = .00 E = .00 }
942 # From A1CH2+HO2
943 R089f: A-C3H5 + HO2 -> C3H5O + OH { A = 1.19E+09 n = 1.03 E = -9.41 }
944
945 R090f: T-C3H5 + H -> P-C3H4 + H2 { A = 3.34E+12 n = .00 E = .00 }
946 R091f: T-C3H5 + O -> CH3 + CH2CO { A = 6.00E+13 n = .00 E = .00 }
947 R092 : T-C3H5 + OH -> CH3 + CH2CO + H { A = 5.00E+12 n = .00 E = .00 }
948 R093 : T-C3H5 + HO2 -> CH3 + CH2CO + OH { A = 2.00E+13 n = .00 E = .00 }
949 R094f: T-C3H5 + HCO -> C3H6 + CO { A = 9.00E+13 n = .00 E = .00 }
950 R095f: T-C3H5 + CH3 -> P-C3H4 + CH4 { A = 1.00E+11 n = .00 E = .00 }
951
952 R096f: S-C3H5 + H -> P-C3H4 + H2 { A = 3.34E+12 n = .00 E = .00 }
953 R097f: S-C3H5 + O -> C2H4 + HCO { A = 6.00E+13 n = .00 E = .00 }
954 R098 : S-C3H5 + OH -> C2H4 + HCO + H { A = 5.00E+12 n = .00 E = .00 }
955 R099 : S-C3H5 + HO2 -> C2H4 + HCO + OH { A = 2.00E+13 n = .00 E = .00 }
956 R100f: S-C3H5 + HCO -> C3H6 + CO { A = 9.00E+13 n = .00 E = .00 }
957 R101f: S-C3H5 + CH3 -> P-C3H4 + CH4 { A = 1.00E+11 n = .00 E = .00 }
958
959 # Adapted from C2H5/C2H3+O2
960 R102f: T-C3H5 + O2 -> A-C3H4 + HO2 { A = 1.92E+07 n = 1.02 E = -8.51 }
961 R103f: T-C3H5 + O2 -> P-C3H4 + HO2 { A = 1.34E+06 n = 1.61 E = -1.61 }
962 R104f: S-C3H5 + O2 -> P-C3H4 + HO2 { A = 6.70E+05 n = 1.61 E = -1.61 }
963 R105 : T-C3H5 + O2 -> CH3 + CO + CH2O { A = 4.58E+16 n = -1.39 E = 4.25 }
964 R106f: S-C3H5 + O2 -> CH3CHO + HCO { A = 4.58E+16 n = -1.39 E = 4.25 }
965
966
967 # Propanone
968 # ---------
969
970 # NC7 path from LLNL
971 R107f: C3H5O -> C2H3CHO + H { A = 1.00E+14 n = .00 E = 121.75 }
972 R108f: C3H5O -> C2H3 + CH2O { A = 2.03E+12 n = 0.09 E = 98.58 }
973 R109f: C3H5O + O2 -> C2H3CHO + HO2 { A = 1.00E+12 n = .00 E = 25.10 }
974
975
976 # Propene
977 # -------
978 # A -> 60%-85% C2H6; S -> 20%-50% C2H4; T -> 35% C2H4
979
980 # Stoliarov et al. 2002
981 # Rates fitted at 1.33 bar - 500K to 2400K
982 R110f: C3H6 -> C2H3 + CH3 { A = 4.04E+42 n = -7.67 E = 467.90 }
983 R111f: C2H3 + CH3 -> A-C3H5 + H { A = 1.93E+18 n = -1.25 E = 32.09 }
984
985 # Harding, Klippenstein, & Georgievskii 2007
986 # -> High pressure limit
987 # Stoliarov et al. 2002
988 # -> Fall-off at 1.33bar - 900K to 3000K
989 R112f: A-C3H5 + H -> C3H6 { A = 5.93E+54 n =-11.76 E = 98.53 }
990
991 # Miller & Klippenstein 2013
992 # Refitted at P=1bar
993 R113f: C3H6 + H -> C2H4 + CH3 { A = 2.67E+12 n = 0.47 E = 22.72 }
994 R114f: C3H6 + H -> A-C3H5 + H2 { A = 1.42E+04 n = 2.82 E = 14.23 }
995 R115f: C3H6 + H -> S-C3H5 + H2 { A = 8.34E+02 n = 3.25 E = 50.86 }
996 R116f: C3H6 + H -> T-C3H5 + H2 { A = 1.49E+02 n = 3.38 E = 37.28 }
997
998 # Zador, Jasper, Miller 2009
999 # Vasu, Hong, Davidson, Hanson 2010
1000 R117f: C3H6 + OH -> A-C3H5 + H2O { A = 9.00E+04 n = 2.59 E = 1.74 }
1001 R118f: C3H6 + OH -> S-C3H5 + H2O { A = 3.67E+03 n = 2.89 E = 8.05 }
1002 R119f: C3H6 + OH -> T-C3H5 + H2O { A = 4.67E+04 n = 2.47 E = 7.31 }
1003
1004 # Adapted from C2H4 - To be revised later
1005 R120f: C3H6 + O -> CH2CHO + CH3 { A = 5.09E+07 n = 1.66 E = 2.75 }
1006 R121f: C3H6 + O -> C2H5 + HCO { A = 1.95E+08 n = 1.36 E = 3.71 }
1007 R122 : C3H6 + O -> C2H3CHO + 2H { A = 3.83E+09 n = 0.88 E = 4.77 }
1008
1009 # Rate from C3H8 + X (x0.5)
1010 R123f: C3H6 + O -> A-C3H5 + OH { A = 9.95E+04 n = 2.68 E = 15.55 }
1011 R124f: C3H6 + HO2 -> A-C3H5 + H2O2 { A = 2.38E+04 n = 2.55 E = 69.00 }
1012 R125f: C3H6 + CH3 -> A-C3H5 + CH4 { A = 4.57E-01 n = 3.65 E = 29.93 }
1013
1014 # From C2H4
1015 R126f: C3H6 + CH3 -> S-C3H5 + CH4 { A = 1.14E+05 n = 2.00 E = 38.49 }
1016 R127f: C3H6 + CH3 -> T-C3H5 + CH4 { A = 5.68E+05 n = 2.00 E = 38.49 }
1017
1018
1019 # Hexadiyene
1020 # ----------
1021
1022 # Lynch, Annesley, Aul, Yang, Tranter 2013
1023 R128f: A-C3H5 + A-C3H5 -> A-C3H4 + C3H6 { A = 7.50E+11 n = .00 E = .00 }
1024 # Matsugi, Suma, Miyoshi 2011
1025 R129 : A-C3H5 + A-C3H5 -> C6H10 { A = 3.18E+13 n = -0.24 E = -2.46 }
1026
1027 # From C3H8 (x2)
1028 R130 : C6H10 + H -> C6H9 + H2 { A = 1.52E+08 n = 1.86 E = 23.43 }
1029 R131 : C6H10 + O -> C6H9 + OH { A = 9.52E+04 n = 2.71 E = 8.81 }
1030 R132 : C6H10 + OH -> C6H9 + H2O { A = 3.62E+05 n = 2.44 E = -2.24 }
1031 R133 : C6H10 + CH3 -> C6H9 + CH4 { A = 3.02E+00 n = 3.46 E = 29.93 }
1032 R134 : C6H10 + HO2 -> C6H9 + H2O2 { A = 1.93E+04 n = 2.60 E = 58.20 }
1033
1034 # From C3H6 (x2)
1035 R135 : C6H10 + H -> C4H7 + C2H4 { A = 5.34E+12 n = 0.47 E = 22.72 }
1036
1037
1038 # Hexadiyenyl radical
1039 # -------------------
1040
1041 # From C2H5
1042 R136 : C6H9 + O -> C2H3CHO + A-C3H5 { A = 3.17E+13 n = 0.03 E = -1.65 }
1043 R137 : C6H9 + HO2 -> C2H3CHO + A-C3H5 + OH { A = 3.10E+13 n = .00 E = .00 }
1044
1045 # From LLNL
1046 R138 : C6H9 -> C4H6 + C2H3 { A = 2.50E+13 n = .00 E = 188.28 }
1047
1048
1049
1050 #==========================================================================#
1051 # #
1052 # "Shock-Tube and Modeling Study of Diacetylene Pyrolysis and Oxidation" #
1053 # Y. Hidaka, Y. Henmi, T. Ohonishi & T. Okuno #
1054 # Combustion and Flame 130:62-82 (2002) #
1055 # #
1056 #==========================================================================#
1057
1058
1059 # Diacetylene
1060 # -----------
1061
1062 # From C2H
1063 H01 : C4H + O2 -> C2H + 2CO { A = 1.00E+13 n = .00 E = -3.16 }
1064
1065 # HT backward rate (1900K) as Frank, Just 1980
1066 # Xu, Braun-Unkhoff, Naumann, Frank 2007
1067 H02f: C4H + H -> C4H2 { A = 3.00E+14 n = .00 E = .00 }
1068
1069 # Adapted from C2H2
1070 H03f: C4H2 + H -> C4H + H2 { A = 3.20E+09 n = 1.80 E = 125.97 }
1071
1072 # Estimated
1073 H04f: C2H + C2H -> C4H2 { A = 1.00E+14 n = .00 E = .00 }
1074
1075 # Ceursters, Nguyen, Peeters, Nguyen 2000
1076 H05f: C2H2 + C2H -> C4H2 + H { A = 7.80E+13 n = .00 E = .00 }
1077
1078 # From P-C3H4 (x2)
1079 H06 : C4H2 + O2 -> C2H + CO + HCO { A = 8.00E+14 n = .00 E = 175.43 }
1080
1081 # Mitchell, Brunning, Payne, Stief 1988
1082 # Rate about x10 that of C2H2 at 298K
1083 # TO BE REVISED
1084 H07f: C4H2 + O -> C3H2 + CO { A = 3.70E+09 n = 1.28 E = 10.34 }
1085
1086 # Klippenstein & Miller 2005
1087 # Refitted Rate & TROE form
1088 H08f: C4H2 + H + M9 -> I-C4H3 + M9 { Ai= 4.31E+10 ni= 1.16 Ei= 7.33
1089 A = 2.30E+45 n = -8.10 E = 10.49
1090 fcA = 0.901 fctA = 12.5
1091 fcB = 0.099 fctB = 10000
1092 fcc = 1.0 fctc = 6674 }
1093 H09f: C4H2 + H -> N-C4H3 { A = 1.37E+39 n = -7.87 E = 64.61 }
1094
1095 # Senosiain, Klippenstein & Miller 2007
1096 H10f: C4H2 + OH -> C4H + H2O { A = 9.15E+09 n = 1.03 E = 90.99 }
1097 H11f: C4H2 + OH -> C4H2O + H { A = 3.41E+10 n = 0.31 E = 5.00 }
1098 H12f: C4H2 + OH -> C3H3 + CO { A = 2.11E+23 n = -3.47 E = 31.76 }
1099
1100
1101 # Ethynylketene
1102 # -------------
1103
1104 # From C4H2+H/OH (HPLx0.5)
1105 H13f: C4H2O + H -> C2H2 + HCCO { A = 6.85E+38 n = -7.87 E = 64.61 }
1106 H14f: C4H2O + OH -> CH2CO + HCCO { A = 1.53E+11 n = 0.47 E = -1.95 }
1107
1108
1109 # C4H3 radicals
1110 # -------------
1111
1112 # Wang & Frenklach 1994 ??
1113 H15f: N-C4H3 -> I-C4H3 { A = 4.10E+43 n = -9.50 E = 221.75 }
1114 H16f: N-C4H3 + H -> I-C4H3 + H { A = 2.50E+20 n = -1.67 E = 45.19 }
1115 H17f: N-C4H3 + H -> C4H4 { A = 2.00E+47 n =-10.26 E = 54.68 }
1116 H18f: I-C4H3 + H -> C4H4 { A = 3.40E+43 n = -9.01 E = 50.71 }
1117 H19f: N-C4H3 + H -> C2H2 + H2C2 { A = 6.30E+25 n = -3.34 E = 41.88 }
1118 H20f: I-C4H3 + H -> C2H2 + H2C2 { A = 2.80E+23 n = -2.55 E = 45.10 }
1119
1120 # From C2H3+X
1121 H21f: N-C4H3 + H -> C4H2 + H2 { A = 1.50E+13 n = .00 E = .00 }
1122 H22f: I-C4H3 + H -> C4H2 + H2 { A = 3.00E+13 n = .00 E = .00 }
1123 H23f: N-C4H3 + OH -> C4H2 + H2O { A = 2.50E+12 n = .00 E = .00 }
1124 H24f: I-C4H3 + OH -> C4H2 + H2O { A = 5.00E+12 n = .00 E = .00 }
1125 H25f: N-C4H3 + O2 -> C4H2 + HO2 { A = 6.70E+05 n = 1.61 E = -1.61 }
1126 H26f: I-C4H3 + O2 -> C4H2 + HO2 { A = 1.34E+06 n = 1.61 E = -1.61 }
1127
1128 H27f: I-C4H3 + O -> CH2CO + C2H { A = 2.00E+13 n = .00 E = .00 }
1129 H28f: I-C4H3 + O2 -> HCCO + CH2CO { A = 1.63E+11 n = .00 E = -7.53 }
1130
1131 # From C3H3 + O2
1132 H29f: I-C4H3 + O2 -> HCO + C2H2 + CO { A = 1.70E+05 n = 1.70 E = 6.28 }
1133
1134
1135 # Vinylacetylene
1136 # --------------
1137
1138 # Decomposition of C4H4 revisited
1139 # Problem for diffusion flamelets with C2H2+H2C2
1140 H30f: C2H3 + C2H -> C4H4 { A = 1.00E+14 n = .00 E = .00 }
1141 H31f: C2H4 + C2H -> C4H4 + H { A = 1.20E+13 n = .00 E = .00 }
1142
1143 # Miller, Klippenstein & Robertson 2000
1144 H32f: C2H3 + C2H2 -> C4H4 + H { A = 1.32E+12 n = 0.16 E = 34.78 }
1145
1146 # Adapted from C2H4 - 3kcal
1147 H33f: C4H4 + H -> N-C4H3 + H2 { A = 1.27E+05 n = 2.75 E = 48.74 }
1148 H34f: C4H4 + H -> I-C4H3 + H2 { A = 6.35E+04 n = 2.75 E = 36.19 }
1149 H35f: C4H4 + OH -> N-C4H3 + H2O { A = 2.23E+04 n = 2.75 E = 9.27 }
1150 H36f: C4H4 + OH -> I-C4H3 + H2O { A = 1.12E+04 n = 2.75 E = -3.28 }
1151 H37f: C4H4 + CH3 -> N-C4H3 + CH4 { A = 1.14E+05 n = 2.00 E = 38.49 }
1152 H38f: C4H4 + CH3 -> I-C4H3 + CH4 { A = 5.68E+04 n = 2.00 E = 25.94 }
1153
1154 # From C2H2
1155 H39f: C4H4 + O -> C2H3 + HCCO { A = 3.70E+09 n = 1.28 E = 10.34 }
1156 # From C2H4 (x1/2)
1157 H40f: C4H4 + O -> C3H2 + CH2O { A = 3.58E+04 n = 2.47 E = 3.89 }
1158 H41f: C4H4 + O -> C3H3 + HCO { A = 1.95E+08 n = 1.36 E = 3.71 }
1159
1160 H42f: C4H4 + OH -> CH2CO + C2H3 { A = 2.10E+01 n = 3.22 E = -1.76 }
1161 H43f: C4H4 + OH -> A-C3H5 + CO { A = 1.28E+09 n = 0.73 E = 10.79 }
1162
1163
1164 # Hexatriyne & Octotetrayne
1165 # -------------------------
1166
1167 # Reactions of C6H2 & C8H2
1168 # Ceursters, Nguyen, Peeters, Nguyen 2000
1169 H44f: C4H2 + C2H -> C6H2 + H { A = 7.80E+13 n = .00 E = .00 }
1170 H45f: C2H2 + C4H -> C6H2 + H { A = 7.80E+13 n = .00 E = .00 }
1171 H46f: C6H2 + C2H -> C8H2 + H { A = 7.80E+13 n = .00 E = .00 }
1172 H47f: C4H2 + C4H -> C8H2 + H { A = 7.80E+13 n = .00 E = .00 }
1173
1174 # Estimated
1175 H48f: C4H + C4H -> C8H2 { A = 1.00E+14 n = .00 E = .00 }
1176
1177 # From C4H2 + OH
1178 H49 : C6H2 + OH -> C4H2 + HCCO { A = 3.41E+10 n = 0.31 E = 5.00 }
1179 H50 : C8H2 + OH -> C6H2 + HCCO { A = 3.41E+10 n = 0.31 E = 5.00 }
1180
1181
1182
1183 #==========================================================================#
1184 # #
1185 # "Detailed kinetic modelling of butadiene Oxidation at high temperatures" #
1186 # A. Laskin, H. Wang, C. Law. #
1187 # Int. J. Chem. Kinet. 2000. 32-589 #
1188 # #
1189 #==========================================================================#
1190
1191
1192 # Butadiene
1193 # ---------
1194
1195 # Baulch et al. 2005
1196 # Full rate to addition
1197 B01f: 2 C2H3 -> C4H6 { A = 8.43E+13 n = .00 E = .00 }
1198
1199 # Ismail, Georgievskii, Taatjes, et al. 2007
1200 # Rates fitted at P=1.33bar
1201 B02f: C2H4 + C2H3 -> C4H6 + H { A = 2.15E+12 n = 0.46 E = 62.65 }
1202
1203 B03f: C3H3 + CH3 + M9 -> C4H6 + M9 { A = 2.60E+57 n =-11.94 E = 40.89
1204 Ai= 1.50E+12 ni= .00 Ei= .00
1205 fcA = 0.825 fctA = 1340.6
1206 fcb = 0.175 fctb = 60000
1207 fcc = 1.0 fctc = 9769.8 }
1208
1209 B04f: C3H6 + C2H3 -> C4H6 + CH3 { A = 7.23E+11 n = .00 E = 20.92 }
1210
1211 # Lumping species 12-C4H6 into C4H6
1212 B05f: P-C3H4 + CH3 -> C4H6 + H { A = 8.94E+07 n = 1.14 E = 51.80 }
1213 B06f: A-C3H4 + CH3 -> C4H6 + H { A = 2.83E+08 n = 1.06 E = 46.70 }
1214
1215 # Wang & Frenklach 1997
1216 B07f: C4H6 -> I-C4H5 + H { A = 5.70E+36 n = -6.27 E = 470.09 }
1217 B08f: C4H6 -> N-C4H5 + H { A = 5.30E+44 n = -8.62 E = 517.18 }
1218 B09f: C4H6 -> C4H4 + H2 { A = 2.50E+15 n = .00 E = 396.22 }
1219
1220 # Adapted from C2H4 - 3kcal
1221 # Rate for OH from Vasu, Hanson, et al. 2010 - refitted
1222 B10f: C4H6 + H -> N-C4H5 + H2 { A = 1.27E+05 n = 2.75 E = 48.74 }
1223 B11f: C4H6 + H -> I-C4H5 + H2 { A = 6.35E+04 n = 2.75 E = 36.19 }
1224 B12f: C4H6 + OH -> N-C4H5 + H2O { A = 1.56E+05 n = 2.46 E = 7.78 }
1225 B13f: C4H6 + OH -> I-C4H5 + H2O { A = 2.17E+06 n = 2.08 E = 6.58 }
1226 B14f: C4H6 + CH3 -> N-C4H5 + CH4 { A = 2.06E-01 n = 3.94 E = 51.98 }
1227 B15f: C4H6 + CH3 -> I-C4H5 + CH4 { A = 1.03E-01 n = 3.94 E = 39.43 }
1228
1229 B16f: C4H6 + C2H3 -> N-C4H5 + C2H4 { A = 5.00E+13 n = .00 E = 95.54 }
1230 B17f: C4H6 + C2H3 -> I-C4H5 + C2H4 { A = 2.50E+13 n = .00 E = 82.84 }
1231
1232 # From C2H4 + O
1233 B18 : C4H6 + O -> A-C3H5 + CO + H { A = 7.66E+09 n = 0.88 E = 4.77 }
1234 B19f: C4H6 + O -> P-C3H4 + CH2O { A = 7.15E+04 n = 2.47 E = 3.89 }
1235 B20f: C4H6 + O -> A-C3H5 + HCO { A = 3.89E+08 n = 1.36 E = 3.71 }
1236
1237
1238 # Butadienyl radicals
1239 # -------------------
1240
1241 # Wang & Frenklach 1994
1242 B21f: C2H3 + C2H2 -> N-C4H5 { A = 9.30E+38 n = -8.76 E = 50.21 }
1243
1244 # Wang & Frenklach 1997
1245 B22f: 2 C2H3 -> I-C4H5 + H { A = 1.20E+22 n = -2.44 E = 57.13 }
1246 B23f: 2 C2H3 -> N-C4H5 + H { A = 2.40E+20 n = -2.04 E = 64.28 }
1247 B24f: 2 C2H3 -> C2H2 + C2H4 { A = 9.60E+11 n = .00 E = .00 }
1248
1249 # Wang & Frenklach 1994
1250 B25f: C4H4 + H -> N-C4H5 { A = 1.30E+51 n =-11.92 E = 69.04 }
1251 B26f: C4H4 + H -> I-C4H5 { A = 4.90E+51 n =-11.92 E = 74.06 }
1252 B27f: N-C4H5 -> I-C4H5 { A = 1.50E+67 n =-16.89 E = 247.30 }
1253
1254 # Wang & Frenklach 1997
1255 B28f: N-C4H5 + H -> I-C4H5 + H { A = 3.10E+26 n = -3.35 E = 72.90 }
1256
1257 B29f: N-C4H5 + H -> C4H4 + H2 { A = 1.50E+13 n = .00 E = .00 }
1258 B30f: N-C4H5 + OH -> C4H4 + H2O { A = 2.50E+12 n = .00 E = .00 }
1259 B31f: N-C4H5 + HCO -> C4H6 + CO { A = 5.00E+12 n = .00 E = .00 }
1260 B32f: N-C4H5 + H2O2 -> C4H6 + HO2 { A = 1.21E+10 n = .00 E = -2.49 }
1261 B33f: N-C4H5 + HO2 -> C4H6 + O2 { A = 6.00E+11 n = .00 E = .00 }
1262
1263 # From C2H3 + O
1264 B34f: N-C4H5 + O -> A-C3H5 + CO { A = 1.03E+13 n = 0.21 E = -1.79 }
1265
1266 # From C2H3 + O2
1267 B35f: N-C4H5 + O2 -> C4H4 + HO2 { A = 6.70E+05 n = 1.61 E = -1.61 }
1268 B36 : N-C4H5 + O2 -> A-C3H5 + CO + O { A = 3.03E+11 n = 0.29 E = 0.05 }
1269 B37f: N-C4H5 + O2 -> HCO + C2H3CHO { A = 4.58E+16 n = -1.39 E = 4.25 }
1270
1271 B38f: I-C4H5 + H -> C4H4 + H2 { A = 3.00E+13 n = .00 E = .00 }
1272 B39f: I-C4H5 + H -> C3H3 + CH3 { A = 2.00E+13 n = .00 E = 8.37 }
1273 B40f: I-C4H5 + OH -> C4H4 + H2O { A = 5.00E+12 n = .00 E = .00 }
1274 B41f: I-C4H5 + HCO -> C4H6 + CO { A = 5.00E+12 n = .00 E = .00 }
1275 B42f: I-C4H5 + HO2 -> C4H6 + O2 { A = 6.00E+11 n = .00 E = .00 }
1276 B43f: I-C4H5 + H2O2 -> C4H6 + HO2 { A = 1.21E+10 n = .00 E = -2.49 }
1277 B44f: I-C4H5 + O2 -> CH2CO + CH2CHO { A = 2.16E+10 n = .00 E = 10.46 }
1278
1279 # From C2H5 + O
1280 B45f: I-C4H5 + O -> C3H3 + CH2O { A = 3.17E+13 n = 0.03 E = -1.65 }
1281
1282 B46f: N-C4H5 + C2H3 -> A1-C6H6 + H2 { A = 1.84E-13 n = 7.07 E = -15.11 }
1283
1284
1285
1286 #==========================================================================#
1287 # #
1288 # "A Detailed Chemical Kinetic Reaction Mechanism for #
1289 # n-Alkane Hydrocarbons from n-Octane to n-Hexadecane" #
1290 # C. K. Westbrook, W. J. Pitz, O. Herbinet, H. J. Curran and E. J. Silke #
1291 # Combustion and Flame 156:181-199 (2009). #
1292 # #
1293 # LLNL-MI-407455 - version dated 2008-09-02 C.K. Westbrook #
1294 # #
1295 #==========================================================================#
1296
1297
1298 # ------------------- HIGH TEMPERATURE -------------------- #
1299 # ---------------------- 3 Species ------------------------ #
1300 # --------------------- 17 Reactions ---------------------- #
1301
1302 # Reactions of N-C6H14
1303
1304 HX01 : N-C6H14 -> N-C5H11 + CH3 { A = 6.03E+18 n = -0.67 E = 362.13 }
1305 HX02 : N-C6H14 -> N-C4H9 + C2H5 { A = 1.62E+22 n = -1.49 E = 364.80 }
1306 HX03 : N-C6H14 -> N-C3H7 + N-C3H7 { A = 2.62e+22 n = -1.56 E = 367.94 }
1307
1308 HX04 : N-C6H14 + H -> C6H13 + H2 { A = 6.16E+07 n = 2.10 E = 22.91 }
1309 HX05 : N-C6H14 + O -> C6H13 + OH { A = 1.42E+06 n = 2.56 E = 12.62 }
1310 HX06 : N-C6H14 + OH -> C6H13 + H2O { A = 7.49E+06 n = 2.09 E = -2.61 }
1311 HX07 : N-C6H14 + O2 -> C6H13 + HO2 { A = 1.70E+13 n = 0.20 E = 209.99 }
1312 HX08 : N-C6H14 + HO2 -> C6H13 + H2O2 { A = 6.27E+12 n = 0.21 E = 74.05 }
1313
1314 # Reactions of C6H13 (lumped)
1315 # Branching ratios 0.2/0.4
1316
1317 HX09 : C6H13 -> N-C4H9 + C2H4 { A = 3.20E+12 n = 0.13 E = 120.84 }
1318 HX10 : C6H13 -> N-C3H7 + C3H6 { A = 5.52E+12 n = 0.17 E = 125.16 }
1319 HX11 : C6H13 -> C2H5 + C4H8 { A = 2.76E+12 n = 0.17 E = 125.16 }
1320 HX12 : C6H13 -> CH3 + C5H10 { A = 2.76E+12 n = 0.17 E = 125.16 }
1321
1322 HX13 : C6H13 -> C6H12 + H { A = 1.78E+08 n = 1.63 E = 144.24 }
1323
1324 HX14 : C6H13 + HO2 -> C6H13O + OH { A = 7.00E+12 n = .00 E = -4.18 }
1325 HX15 : C6H13 + CH3O2 -> C6H13O + CH3O { A = 7.00E+12 n = .00 E = -4.18 }
1326
1327 # Reactions of C6H13O
1328
1329 HX16 : C6H13O -> N-C5H11 + CH2O { A = 1.19E+18 n = -1.50 E = 84.44 }
1330 HX17 : C6H13O -> N-C4H9 + CH3CHO { A = 7.16E+22 n = -2.78 E = 96.22 }
1331 HX18 : C6H13O -> N-C3H7 + C2H5 + HCO { A = 4.10E+17 n = -1.31 E = 81.60 }
1332
1333
1334
1335 # ------------------- LOW TEMPERATURE -------------------- #
1336 # ---------------------- 5 Species ----------------------- #
1337 # -------------------- 11 Reactions ---------------------- #
1338
1339 /* Commented for now
1340
1341 # Formation of ROO
1342
1343 HX20 : C6H13 + O2 -> C6H13O2 { A = 1.36E+13 n = -0.08 E = 0.87 }
1344 HX21 : C6H13O2 -> C6H13 + O2 { A = 1.71E+23 n = -2.33 E = 158.32 }
1345 HX22 : C6H13O2 -> C6H12OOH { A = 1.83E+05 n = 1.70 E = 80.90 }
1346
1347 # Reactions of QOOH
1348
1349 HX23 : C6H12OOH -> C6H13O2 { A = 7.53E+04 n = 1.25 E = 24.89 }
1350 HX24 : C6H12OOH -> C6H12 + HO2 { A = 4.01E+00 n = 3.28 E = 53.36 }
1351 HX25 : C6H12OOH -> C6H12O + OH { A = 1.33E+12 n = -0.74 E = 42.56 }
1352 HX26 : C6H12OOH + O2 -> C6H13O4 { A = 7.71E+12 n = -0.01 E = -0.06 }
1353
1354 # Reactions of O2QOOH
1355
1356 HX27 : C6H13O4 -> C6H12OOH + O2 { A = 2.31E+21 n = -1.97 E = 153.05 }
1357 HX28 : C6H13O4 -> OC6H11OOH + OH { A = 6.47E+09 n = 0.18 E = 83.01 }
1358
1359 # Reactions of OQ'OOH
1360 # all products lumped
1361
1362 HX29: OC6H11OOH -> C5H10 + CH2CO + OH { A = 3.26E+09 n = 1.93 E = 161.11 }
1363
1364 # Reactions of QO
1365 # all products lumped
1366
1367 HX30: C6H12O + OH -> N-C4H9 + CH2CO + H2O { A = 3.68E+12 n = .00 E = .00 }
1368 */
1369
1370
1371 #==========================================================================#
1372 # #
1373 # "A Comprehensive Modeling Study of n-Heptane Oxidation" #
1374 # Curran, H. J., Gaffuri, P., Pitz, W. J., and Westbrook, C. K. #
1375 # Combustion and Flame 114:149-177 (1998). #
1376 # #
1377 # UCRL-WEB-204236 - Review and release date: May 19, 2004. #
1378 # #
1379 #==========================================================================#
1380
1381
1382 # ------------------- HIGH TEMPERATURE -------------------- #
1383 # ---------------------- 3 Species ------------------------ #
1384 # --------------------- 19 Reactions ---------------------- #
1385
1386 # Reactions of N-C7H16
1387
1388 # Rates from LLNL
1389 # Multiplied by 3 to match overall decomp rate from exp
1390 # (Davidson, Oehlschlaeger, Hanson 2007)
1391 HP01 : N-C7H16 -> N-C6H13 + CH3 { A = 8.79E+73 n =-16.61 E = 497.48 }
1392 HP02 : N-C7H16 -> N-C5H11 + C2H5 { A = 2.43E+78 n =-17.62 E = 503.75 }
1393 HP03 : N-C7H16 -> N-C4H9 + N-C3H7 { A = 4.26E+78 n =-17.71 E = 505.01 }
1394
1395 HP04 : N-C7H16 + H -> C7H15 + H2 { A = 9.90E+07 n = 2.06 E = 22.98 }
1396 HP05 : N-C7H16 + O -> C7H15 + OH { A = 1.72E+05 n = 2.81 E = 9.46 }
1397 HP06 : N-C7H16 + OH -> C7H15 + H2O { A = 9.68E+06 n = 2.08 E = -2.73 }
1398 HP07 : N-C7H16 + O2 -> C7H15 + HO2 { A = 2.89E+13 n = 0.20 E = 209.66 }
1399 HP08 : N-C7H16 + HO2 -> C7H15 + H2O2 { A = 7.57E+12 n = 0.21 E = 73.78 }
1400
1401 # Reactions of C7H15 (lumped)
1402 # Branching ratios 0.17/0.33/0.17
1403 # NEW Branching ratios from OH rate about the same at 1000K
1404
1405 HP09 : C7H15 -> N-C5H11 + C2H4 { A = 2.72E+12 n = 0.13 E = 120.84 }
1406 HP10 : C7H15 -> N-C4H9 + C3H6 { A = 4.55E+12 n = 0.17 E = 125.16 }
1407 HP11 : C7H15 -> N-C3H7 + C4H8 { A = 2.28E+12 n = 0.17 E = 125.16 }
1408 HP12 : C7H15 -> C2H5 + C5H10 { A = 2.35E+12 n = 0.17 E = 125.16 }
1409 HP13 : C7H15 -> CH3 + C6H12 { A = 2.28E+12 n = 0.17 E = 125.16 }
1410
1411 HP14 : C7H15 -> C7H14 + H { A = 1.78E+08 n = 1.63 E = 144.24 }
1412
1413 HP15 : C7H15 + HO2 -> C7H15O + OH { A = 7.00E+12 n = .00 E = -4.18 }
1414 HP16 : C7H15 + CH3O2 -> C7H15O + CH3O { A = 7.00E+12 n = .00 E = -4.18 }
1415
1416 # Reactions of C7H15O (lumped)
1417
1418 HP17 : C7H15O -> N-C5H11 + CH3CHO { A = 8.92E+19 n = -2.03 E = 87.88 }
1419 HP18 : C7H15O -> N-C4H9 + C2H5 + HCO { A = 2.23E+15 n = -0.70 E = 77.85 }
1420 HP19 : C7H15O -> N-C3H7 + N-C3H7 + HCO { A = 6.18E+16 n = -1.36 E = 77.48 }
1421
1422
1423 # ------------------- LOW TEMPERATURE -------------------- #
1424 # ---------------------- 5 Species ----------------------- #
1425 # -------------------- 11 Reactions ---------------------- #
1426
1427 /* Commented for now
1428
1429 # Formation of ROO
1430
1431 HP20: C7H15 + O2 -> C7H15O2 { A = 1.68E+13 n = -0.11 E = 1.01 }
1432 HP21: C7H15O2 -> C7H15 + O2 { A = 1.92E+22 n = -2.11 E = 156.08 }
1433 HP22: C7H15O2 -> C7H14OOH { A = 1.88E+05 n = 1.68 E = 79.51 }
1434
1435 # Reactions of QOOH
1436
1437 HP23: C7H14OOH -> C7H15O2 { A = 7.64E+05 n = 0.91 E = 25.45 }
1438 HP24: C7H14OOH -> C7H14 + HO2 { A = 5.85E+03 n = 2.40 E = 64.08 }
1439 HP25: C7H14OOH -> C7H14O + OH { A = 3.97E-10 n = 5.69 E = 1.57 }
1440 HP26: C7H14OOH + O2 -> C7H15O4 { A = 1.51E+13 n = -0.09 E = 0.53 }
1441
1442 # Reactions of O2QOOH
1443
1444 HP27: C7H15O4 -> C7H14OOH + O2 { A = 1.71E+22 n = -2.13 E = 155.32 }
1445 HP28: C7H15O4 -> OC7H13OOH + OH { A = 4.25E+10 n = -0.11 E = 81.48 }
1446
1447 # Reactions of OQ'OOH
1448 # all products lumped
1449
1450 HP29: OC7H13OOH -> N-C3H7 + CH3CHO + CH2CO + OH { A = 3.26E+09 n = 1.93 E = 161.11 }
1451
1452 # Reactions of QO
1453 # all products lumped
1454
1455 HP30: C7H14O + OH -> C5H11 + CH2CO + H2O { A = 3.68E+12 n = .00 E = .00 }
1456 */
1457
1458
1459
1460 #==========================================================================#
1461 # #
1462 # "A Detailed Chemical Kinetic Reaction Mechanism for #
1463 # n-Alkane Hydrocarbons from n-Octane to n-Hexadecane" #
1464 # C. K. Westbrook, W. J. Pitz, O. Herbinet, H. J. Curran and E. J. Silke #
1465 # Combustion and Flame 156:181-199 (2009). #
1466 # #
1467 # LLNL-MI-407455 - version dated 2008-09-02 C.K. Westbrook #
1468 # #
1469 #==========================================================================#
1470
1471 # H-abs by H from Cartensen & Dean 2009
1472 # H-abs by OH from Kwok & Atkinson 1995 / Pang, Hanson et al. 2011
1473 # Total decomp rate fitted to McDonald 2012 and Klingbeil et al. 2008
1474 # -> individual rates rescaled with same branching ratios
1475
1476 # ------------------- HIGH TEMPERATURE -------------------- #
1477 # ---------------------- 3 Species ------------------------ #
1478 # --------------------- 73 Reactions ---------------------- #
1479
1480 # Reactions of N-C12H26
1481
1482 DD01 : N-C12H26 -> N-C10H21 + C2H5 { A = 1.68E+24 n = -2.11 E = 368.84 }
1483 DD02 : N-C12H26 -> N-C9H19 + N-C3H7 { A = 2.46E+24 n = -2.12 E = 371.27 }
1484 DD03 : N-C12H26 -> N-C8H17 + N-C4H9 { A = 1.21E+24 n = -2.07 E = 369.64 }
1485 DD04 : N-C12H26 -> N-C7H15 + N-C5H11 { A = 1.13E+24 n = -2.06 E = 369.58 }
1486 DD05 : N-C12H26 -> N-C6H13 + N-C6H13 { A = 2.59E+24 n = -2.12 E = 369.69 }
1487
1488 DD06 : N-C12H26 + H -> C12H25 + H2 { A = 3.59E+08 n = 1.97 E = 23.16 }
1489 DD07 : N-C12H26 + O -> C12H25 + OH { A = 3.97E+05 n = 2.76 E = 9.19 }
1490 DD08 : N-C12H26 + OH -> C12H25 + H2O { A = 2.18E+07 n = 2.05 E = -2.95 }
1491 DD09 : N-C12H26 + O2 -> C12H25 + HO2 { A = 1.05E+14 n = 0.10 E = 209.77 }
1492 DD10 : N-C12H26 + HO2 -> C12H25 + H2O2 { A = 2.86E+13 n = 0.11 E = 73.93 }
1493
1494 # Reactions of C12H25 (lumped)
1495 # Branching ratios 0.09/.18
1496 # NEW Branching ratios from OH rate about same at 1000K
1497
1498 DD11 : C12H25 -> N-C10H21 + C2H4 { A = 1.44E+12 n = 0.13 E = 120.84 }
1499 DD12 : C12H25 -> N-C9H19 + C3H6 { A = 2.48E+12 n = 0.17 E = 125.16 }
1500 DD13 : C12H25 -> N-C8H17 + C4H8 { A = 2.48E+12 n = 0.17 E = 125.16 }
1501 DD14 : C12H25 -> N-C7H15 + C5H10 { A = 1.24E+12 n = 0.17 E = 125.16 }
1502 DD15 : C12H25 -> N-C6H13 + C6H12 { A = 1.24E+12 n = 0.17 E = 125.16 }
1503 DD16 : C12H25 -> N-C5H11 + C7H14 { A = 1.24E+13 n = 0.17 E = 125.16 }
1504 DD17 : C12H25 -> N-C4H9 + C8H16 { A = 1.24E+13 n = 0.17 E = 125.16 }
1505 DD18 : C12H25 -> N-C3H7 + C9H18 { A = 1.24E+12 n = 0.17 E = 125.16 }
1506 DD19 : C12H25 -> C2H5 + C10H20 { A = 1.24E+12 n = 0.17 E = 125.16 }
1507
1508 DD20 : C12H25 -> C12H24 + H { A = 1.78E+08 n = 1.63 E = 144.24 }
1509
1510 DD21 : C12H25 + HO2 -> C12H25O + OH { A = 7.00E+12 n = .00 E = -4.18 }
1511 DD22 : C12H25 + CH3O2 -> C12H25O + CH3O { A = 7.00E+12 n = .00 E = -4.18 }
1512
1513 # Reactions of C12H25O
1514
1515 DD23 : C12H25O -> N-C10H21 + CH3CHO { A = 4.35E+08 n = 1.31 E = 64.79 }
1516 DD24 : C12H25O -> N-C9H19 + C2H5 + HCO { A = 8.37E+18 n = -1.84 E = 82.98 }
1517 DD25 : C12H25O -> N-C8H17 + N-C3H7 + HCO { A = 9.83E+44 n = -9.70 E = 134.38 }
1518 DD26 : C12H25O -> N-C7H15 + N-C4H9 + HCO { A = 8.35E+61 n =-14.50 E = 179.77 }
1519 DD27 : C12H25O -> N-C6H13 + N-C5H11 + HCO { A = 4.63E+64 n =-15.38 E = 182.82 }
1520
1521 # Reactions of C12H24 (lumped)
1522
1523 DD28 : C12H24 -> N-C9H19 + A-C3H5 { A = 9.53E+15 n = -0.18 E = 298.01 }
1524 DD32 : C12H24 -> N-C8H17 + C4H7 { A = 1.87E+15 n = 0.04 E = 296.85 }
1525 DD31 : C12H24 -> N-C7H15 + C5H9 { A = 1.50E+15 n = -0.02 E = 297.10 }
1526 DD30 : C12H24 -> N-C5H11 + C7H13 { A = 2.08E+15 n = -0.04 E = 297.23 }
1527 DD29 : C12H24 -> N-C4H9 + C8H15 { A = 1.51E+13 n = 0.52 E = 294.52 }
1528
1529 DD33 : C12H24 + H -> C12H23 + H2 { A = 3.70E+13 n = .00 E = 16.32 }
1530 DD34 : C12H24 + OH -> C12H23 + H2O { A = 3.00E+13 n = .00 E = 5.15 }
1531
1532 # Reactions of C12H23 (lumped)
1533
1534 DD35 : C12H23 -> C10H19 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1535 DD36 : C12H23 -> C9H17 + C3H6 { A = 1.38E+13 n = 0.17 E = 125.16 }
1536 DD37 : C12H23 -> C8H15 + C4H8 { A = 1.38E+13 n = 0.17 E = 125.16 }
1537 DD38 : C12H23 -> C7H13 + C5H10 { A = 1.38E+13 n = 0.17 E = 125.16 }
1538 DD39 : C12H23 -> C5H9 + C7H14 { A = 1.38E+13 n = 0.17 E = 125.16 }
1539 DD40 : C12H23 -> C4H7 + C8H16 { A = 1.38E+13 n = 0.17 E = 125.16 }
1540 DD41 : C12H23 -> A-C3H5 + C9H18 { A = 1.38E+13 n = 0.17 E = 125.16 }
1541 DD42 : C12H23 -> C2H3 + C10H20 { A = 1.38E+13 n = 0.17 E = 125.16 }
1542
1543
1544
1545
1546 # -------------------- LOW TEMPERATURE -------------------- #
1547 # ----------------------- 10 Species ---------------------- #
1548 # ---------------------- 21 Reactions --------------------- #
1549 /*
1550 # Reactions of C12H25O2
1551 # Backward rate reduced (x1/6)
1552 # to mimic lumping of peroxy species
1553
1554 DD50 : C12H25 + O2 -> C12H25O2 { A = 9.52E+12 n = -0.04 E = 0.23 }
1555 DD51 : C12H25O2 -> C12H25 + O2 { A = 1.52E+22 n = -2.31 E = 156.59 }
1556 DD52 : C12H25O2 -> C12H24OOH { A = 1.13E+06 n = 1.46 E = 80.17 }
1557 DD53 : C12H24OOH -> C12H25O2 { A = 4.47E+21 n = -3.86 E = 58.11 }
1558
1559 # Reactions of C12H24OOH
1560
1561 DD54 : C12H24OOH -> C12H24 + HO2 { A = 2.21E+14 n = -0.81 E = 84.74 }
1562 DD55 : C12H24OOH -> C12H24O + OH { A = 3.25E-11 n = 5.92 E = -7.84 }
1563 DD56 : C12H24OOH + O2 -> C12H25O4 { A = 1.32E+13 n = -0.08 E = 0.47 }
1564
1565 # Reactions of C12H25O4
1566
1567 DD57 : C12H25O4 -> C12H24OOH + O2 { A = 1.92E+23 n = -2.42 E = 157.60 }
1568 DD58 : C12H25O4 -> C12H24O3 + OH { A = 1.28E+07 n = 0.89 E = 72.18 }
1569
1570 # Reactions of C12H24O3
1571 # lump all decomposition pathways
1572
1573 DD59 : C12H24O3 -> N-C8H17 + CH3CHO + CH2CO + OH{ A = 8.95E+14 n = 0.32 E = 171.10 }
1574
1575 # Reactions of C12H24O
1576 # lump all decomposition pathways
1577
1578 DD60 : C12H24O + OH -> N-C8H17 + C2H4 + CH2CO + H2O{ A = 3.09E+13 n = -0.27 E = 1.61 }
1579
1580 # Reactions of C8H17O2
1581
1582 DD61 : N-C8H17 + O2 -> C8H17O2 { A = 1.65E+22 n = -2.85 E = 19.78 }
1583 DD62 : C8H17O2 -> N-C8H17 + O2 { A = 2.48E+21 n = -1.94 E = 150.73 }
1584 DD63 : C8H17O2 -> C8H16OOH { A = 1.11E+06 n = 1.40 E = 79.77 }
1585
1586 # Reactions of C8H16OOH
1587
1588 DD64 : C8H16OOH -> C8H16O + OH { A = 3.07E+02 n = 2.15 E = 24.57 }
1589 DD65 : C8H16OOH -> C8H16 + HO2 { A = 5.11E+06 n = 1.40 E = 70.08 }
1590 DD66 : C8H16OOH + O2 -> C8H17O4 { A = 1.16E+11 n = 0.53 E = -3.58 }
1591
1592 # Reactions of C8H17O4/C8H16O3
1593
1594 DD67 : C8H17O4 -> C8H16OOH + O2 { A = 1.37E+23 n = -2.37 E = 157.49 }
1595 DD68 : C8H17O4 -> C8H16O3 + OH { A = 9.98E+06 n = 1.02 E = 83.92 }
1596 DD69 : C8H16O3 -> N-C4H9 + CH3CHO + CH2CO + OH { A = 4.44E+32 n = -4.98 E = 207.98 }
1597
1598 DD70 : C8H16O + OH -> N-C6H13 + CH2CO + H2O { A = 3.09E+13 n = -0.27 E = 1.61 }
1599 */
1600
1601
1602
1603 #==========================================================================#
1604 # #
1605 # Additional n-alkyl mechanism #
1606 # (based on) #
1607 # Lawrence Livermore n-Alkanes Mechanism - ver 2 #
1608 # #
1609 #==========================================================================#
1610
1611
1612 # ------------------- HIGH TEMPERATURE -------------------- #
1613 # ---------------------- 21 Species ----------------------- #
1614 # --------------------- 70 Reactions ---------------------- #
1615
1616 # H-abstractions from Miller & Klippenstein 2013 - HPL
1617 # p -> { A = 1.78E+08 n = 1.63 E = 144.24 }
1618 # Beta scissions from Ratkiewicz & Truong 2012 - HPL
1619 # p -> { A = 1.60E+13 n = 0.13 E = 120.84 }
1620 # st -> { A = 1.38E+13 n = 0.17 E = 125.16 }
1621 # H-abstraction for alkane from Cartensen & Dean 2009
1622 # p -> { A = 1.40E+07 n = 1.97 E = 34.31 }
1623 # s -> { A = 3.80E+07 n = 1.86 E = 23.43 }
1624
1625
1626 # Decyl radical
1627 # -------------
1628
1629 # Reactions of N-C10H21
1630
1631 NC01 : N-C10H21 -> N-C8H17 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1632 NC02 : N-C10H21 -> C10H20 + H { A = 2.04E+10 n = 0.95 E = 141.45 }
1633
1634 # Reactions of C10H20
1635
1636 NC03 : C10H20 -> N-C7H15 + A-C3H5 { A = 1.00E+16 n = .00 E = 297.06 }
1637
1638 NC04 : C10H20 + H -> C10H19 + H2 { A = 3.70E+13 n = .00 E = 16.32 }
1639 NC05 : C10H20 + OH -> C10H19 + H2O { A = 3.00E+13 n = .00 E = 5.15 }
1640
1641 # Reactions of C10H19 (lumped)
1642
1643 NC06 : C10H19 -> C8H15 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1644 NC07 : C10H19 -> C7H13 + C3H6 { A = 1.38E+13 n = 0.17 E = 125.16 }
1645 NC08 : C10H19 -> C6H11 + C4H8 { A = 1.38E+13 n = 0.17 E = 125.16 }
1646 NC09 : C10H19 -> C5H9 + C5H10 { A = 1.38E+13 n = 0.17 E = 125.16 }
1647 NC10 : C10H19 -> C4H7 + C6H12 { A = 1.38E+13 n = 0.17 E = 125.16 }
1648 NC11 : C10H19 -> A-C3H5 + C7H14 { A = 1.38E+13 n = 0.17 E = 125.16 }
1649 NC12 : C10H19 -> C2H3 + C8H16 { A = 1.38E+13 n = 0.17 E = 125.16 }
1650
1651
1652 # Nonyl radical
1653 # -------------
1654
1655 # Reactions of N-C9H19
1656
1657 NC13 : N-C9H19 -> N-C7H15 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1658 NC14 : N-C9H19 -> C9H18 + H { A = 2.04E+10 n = 0.95 E = 141.45 }
1659
1660 # Reactions of C9H18
1661
1662 NC15 : C9H18 -> N-C6H13 + A-C3H5 { A = 1.00E+16 n = .00 E = 297.06 }
1663
1664 NC16 : C9H18 + H -> C9H17 + H2 { A = 3.70E+13 n = .00 E = 16.32 }
1665 NC17 : C9H18 + OH -> C9H17 + H2O { A = 3.00E+13 n = .00 E = 5.15 }
1666
1667 # Reactions of C9H17 (lumped)
1668
1669 NC18 : C9H17 -> C7H13 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1670 NC19 : C9H17 -> C6H11 + C3H6 { A = 1.38E+13 n = 0.17 E = 125.16 }
1671 NC20 : C9H17 -> C5H9 + C4H8 { A = 1.38E+13 n = 0.17 E = 125.16 }
1672 NC21 : C9H17 -> C4H7 + C5H10 { A = 1.38E+13 n = 0.17 E = 125.16 }
1673 NC22 : C9H17 -> A-C3H5 + C6H12 { A = 1.38E+13 n = 0.17 E = 125.16 }
1674 NC23 : C9H17 -> C2H3 + C7H14 { A = 1.38E+13 n = 0.17 E = 125.16 }
1675
1676
1677 # Octyl radical
1678 # -------------
1679
1680 # Reactions of N-C8H17
1681
1682 NC24 : N-C8H17 -> N-C6H13 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1683 NC25 : N-C8H17 -> C8H16 + H { A = 2.04E+10 n = 0.95 E = 141.45 }
1684
1685 # Reactions of C8H16
1686
1687 NC26 : C8H16 -> N-C5H11 + A-C3H5 { A = 1.00E+16 n = .00 E = 297.06 }
1688
1689 NC27 : C8H16 + H -> C8H15 + H2 { A = 3.70E+13 n = .00 E = 16.32 }
1690 NC28 : C8H16 + OH -> C8H15 + H2O { A = 3.00E+13 n = .00 E = 5.15 }
1691
1692 # Reactions of C8H15 (lumped)
1693
1694 NC29 : C8H15 -> C6H11 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1695 NC30 : C8H15 -> C5H9 + C3H6 { A = 1.38E+13 n = 0.17 E = 125.16 }
1696 NC31 : C8H15 -> C4H7 + C4H8 { A = 1.38E+13 n = 0.17 E = 125.16 }
1697 NC32 : C8H15 -> A-C3H5 + C5H10 { A = 1.38E+13 n = 0.17 E = 125.16 }
1698 NC33 : C8H15 -> C2H3 + C6H12 { A = 1.38E+13 n = 0.17 E = 125.16 }
1699
1700
1701 # Heptyl radical
1702 # --------------
1703
1704 # Reactions of N-C7H15
1705
1706 NC34 : N-C7H15 -> N-C5H11 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1707 NC35 : N-C7H15 -> C7H14 + H { A = 2.04E+10 n = 0.95 E = 141.45 }
1708
1709 # Reactions of C7H14
1710
1711 NC36 : C7H14 -> N-C4H9 + A-C3H5 { A = 1.00E+16 n = .00 E = 297.06 }
1712
1713 NC37 : C7H14 + H -> C7H13 + H2 { A = 3.70E+13 n = .00 E = 16.32 }
1714 NC38 : C7H14 + OH -> C7H13 + H2O { A = 3.00E+13 n = .00 E = 5.15 }
1715
1716 # Reactions of C7H13 (lumped)
1717
1718 NC39 : C7H13 -> C5H9 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1719 NC40 : C7H13 -> C4H7 + C3H6 { A = 1.38E+13 n = 0.17 E = 125.16 }
1720 NC41 : C7H13 -> A-C3H5 + C4H8 { A = 1.38E+13 n = 0.17 E = 125.16 }
1721 NC42 : C7H13 -> C2H3 + C5H10 { A = 1.38E+13 n = 0.17 E = 125.16 }
1722
1723
1724 # Hexyl radical
1725 # -------------
1726
1727 # Reactions of N-C6H13
1728
1729 NC43 : N-C6H13 -> N-C4H9 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1730 NC44 : N-C6H13 -> C6H12 + H { A = 2.04E+10 n = 0.95 E = 141.45 }
1731
1732 # Reactions of C6H12
1733
1734 NC45 : C6H12 -> N-C3H7 + A-C3H5 { A = 8.52E+26 n = -3.39 E = 320.10 }
1735
1736 NC46 : C6H12 + H -> C6H11 + H2 { A = 3.70E+13 n = .00 E = 16.32 }
1737 NC47 : C6H12 + OH -> C6H11 + H2O { A = 3.00E+13 n = .00 E = 5.15 }
1738
1739 # Reactions of C6H11 (lumped)
1740
1741 NC48 : C6H11 -> C4H7 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1742 NC49 : C6H11 -> A-C3H5 + C3H6 { A = 1.38E+13 n = 0.17 E = 125.16 }
1743 NC50 : C6H11 -> C2H3 + C4H8 { A = 1.38E+13 n = 0.17 E = 125.16 }
1744
1745
1746 # Pentyl radical
1747 # --------------
1748
1749 # Reactions of N-C5H11
1750
1751 NC51 : N-C5H11 -> N-C3H7 + C2H4 { A = 3.24E+12 n = 0.32 E = 120.53 }
1752 NC52 : N-C5H11 -> C3H6 + C2H5 { A = 1.15E+01 n = 3.03 E = 64.07 }
1753 NC53 : N-C5H11 -> C5H10 + H { A = 2.04E+10 n = 0.95 E = 141.45 }
1754
1755 # Reactions of C5H10
1756
1757 NC54 : C5H10 -> A-C3H5 + C2H5 { A = 1.00E+16 n = .00 E = 297.06 }
1758
1759 NC55 : C5H10 + H -> C5H9 + H2 { A = 3.70E+13 n = .00 E = 16.32 }
1760 NC56 : C5H10 + OH -> C5H9 + H2O { A = 3.00E+13 n = .00 E = 5.15 }
1761
1762 # Reactions of C5H9 (lumped)
1763
1764 NC57 : C5H9 -> A-C3H5 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1765 NC58 : C5H9 -> C2H3 + C3H6 { A = 1.38E+13 n = 0.17 E = 125.16 }
1766
1767
1768 # Butyl radical
1769 # -------------
1770
1771 # Reactions of N-C4H9
1772
1773 NC59 : N-C4H9 -> C2H5 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1774 NC60 : N-C4H9 -> C4H8 + H { A = 2.04E+10 n = 0.95 E = 141.45 }
1775
1776 # Reactions of C4H8 reactions
1777
1778 NC61 : C4H8 -> A-C3H5 + CH3 { A = 1.00E+16 n = .00 E = 297.06 }
1779
1780 NC62 : C4H8 + H -> C4H7 + H2 { A = 3.70E+13 n = .00 E = 16.32 }
1781 NC63 : C4H8 + OH -> C4H7 + H2O { A = 3.00E+13 n = .00 E = 5.15 }
1782
1783 # Reactions of C4H7
1784
1785 NC64 : C4H7 -> C2H4 + C2H3 { A = 1.00E+11 n = .00 E = 154.81 }
1786 NC65 : C4H7 -> C4H6 + H { A = 1.20E+14 n = .00 E = 206.27 }
1787
1788 NC66 : C4H7 + H -> C4H6 + H2 { A = 3.16E+13 n = .00 E = .00 }
1789 NC67 : C4H7 + O2 -> C4H6 + HO2 { A = 1.00E+09 n = .00 E = .00 }
1790 NC68 : C4H7 + CH3 -> C4H6 + CH4 { A = 8.00E+12 n = .00 E = .00 }
1791
1792 NC69 : C4H7 + HO2 -> A-C3H5 + CH2O + OH { A = 7.00E+12 n = .00 E = -4.18 }
1793 NC70 : C4H7 + CH3O2 -> A-C3H5 + CH2O + CH3O { A = 7.00E+12 n = .00 E = -4.18 }
1794
1795
1796
1797
1798 #==========================================================================#
1799 # #
1800 # M. Mehl, H. J. Curran, W. J. Pitz, and C. K. Westbrook, 2009 #
1801 # LLNL-MI-421507 - Review and release date: December 16, 2009 #
1802 # #
1803 #==========================================================================#
1804
1805
1806 # ------------------- HIGH TEMPERATURE -------------------- #
1807 # ---------------------- 15 Species ----------------------- #
1808 # --------------------- 73 Reactions ---------------------- #
1809
1810 # Reactions of I-C8H18
1811
1812 IC00 : I-C8H18 -> Y-C7H15 + CH3 { A = 6.18E+25 n = -2.46 E = 350.24 }
1813 IC01 : I-C8H18 -> T-C4H8 + I-C3H7 + CH3 { A = 2.46E+23 n = -2.01 E = 348.95 }
1814 IC02 : I-C8H18 -> 2 T-C4H9 { A = 7.83E+29 n = -3.93 E = 352.08 }
1815
1816 IC03 : I-C8H18 + H -> C-C8H17 + H2 { A = 9.08E+00 n = 4.12 E = 7.45 }
1817 IC04 : I-C8H18 + O -> C-C8H17 + OH { A = 4.69E+03 n = 3.19 E = 4.52 }
1818 IC05 : I-C8H18 + OH -> C-C8H17 + H2O { A = 2.70E+05 n = 2.43 E = -4.04 }
1819 IC06 : I-C8H18 + O2 -> C-C8H17 + HO2 { A = 1.03E+11 n = 0.84 E = 196.29 }
1820 IC07 : I-C8H18 + CH3 -> C-C8H17 + CH4 { A = 1.14E-18 n = 9.25 E = -8.89 }
1821 IC08 : I-C8H18 + HO2 -> C-C8H17 + H2O2 { A = 9.85E+10 n = 0.73 E = 70.89 }
1822 IC09 : I-C8H18 + CH3O2 -> C-C8H17 + CH3O + OH { A = 9.85E+10 n = 0.73 E = 70.89 }
1823
1824 # Reactions of C-C8H17
1825
1826 IC10 : C-C8H17 -> Y-C7H14 + CH3 { A = 2.55E+39 n = -7.47 E = 189.48 }
1827 IC11 : C-C8H17 -> T-C4H9 + T-C4H8 { A = 4.28E+22 n = -2.81 E = 127.70 }
1828 IC12 : C-C8H17 -> T-C4H8 + CH3 + C3H6 { A = 4.22E+24 n = -3.34 E = 158.66 }
1829
1830 IC13 : C-C8H17 + HO2 -> D-C8H17O + OH { A = 7.00E+12 n = .00 E = -4.18 }
1831 IC14 : C-C8H17 + CH3O2 -> D-C8H17O + CH3O { A = 7.00E+12 n = .00 E = -4.18 }
1832
1833 # Reactions of D-C8H17O
1834
1835 IC15 : D-C8H17O -> T-C4H8 + CH3 + CH3COCH3 { A = 1.33E+23 n = -2.98 E = 64.44 }
1836 IC16 : D-C8H17O -> T-C4H9 + I-C3H7 + HCO { A = 7.95E+33 n = -6.00 E = 97.57 }
1837 IC17 : D-C8H17O -> Y-C7H15 + CH2O { A = 2.69E+20 n = -2.08 E = 62.99 }
1838
1839 # Reactions of Y-C7H15
1840
1841 IC18 : Y-C7H15 -> T-C4H9 + C3H6 { A = 5.14E+23 n = -2.93 E = 131.78 }
1842 IC19 : Y-C7H15 -> T-C4H8 + I-C3H7 { A = 5.87E+21 n = -2.57 E = 136.80 }
1843 IC20 : Y-C7H15 -> Y-C7H14 + H { A = 6.13E+13 n = 0.03 E = 153.44 }
1844
1845 # Reactions of Y-C7H14
1846
1847 IC21 : Y-C7H14 -> T-C4H9 + A-C3H5 { A = 3.98E+26 n = -3.48 E = 320.14 }
1848 IC22 : Y-C7H14 -> T-C4H7 + I-C3H7 { A = 5.29E+24 n = -2.55 E = 317.38 }
1849
1850 IC23 : Y-C7H14 + H -> X-C7H13 + H2 { A = 2.38E-13 n = 7.67 E = -47.65 }
1851 IC24 : Y-C7H14 + OH -> X-C7H13 + H2O { A = 7.76E-09 n = 6.18 E = -41.33 }
1852
1853 # Reactions of X-C7H13
1854
1855 IC25 : X-C7H13 -> T-C4H9 + A-C3H4 { A = 8.71E+21 n = -2.43 E = 249.07 }
1856 IC26 : X-C7H13 -> T-C4H8 + T-C3H5 { A = 6.32E+18 n = -1.80 E = 182.42 }
1857 IC27 : X-C7H13 -> T-C4H7 + C3H6 { A = 2.10E+16 n = -1.09 E = 74.56 }
1858
1859 #C28 : X-C7H13 + HO2 -> I-C3H5CHO + I-C3H7 + OH { A = 1.00E+13 n = .00 E = .00 }
1860
1861 # Reactions of T-C4H9
1862
1863 # Ratkeiwicz 2011 (x0.5 for lumping)
1864 IC29 : T-C4H9 -> C3H6 + CH3 { A = 3.30E+12 n = 0.37 E = 128.58 }
1865
1866 IC30 : T-C4H9 -> T-C4H8 + H { A = 5.35E+10 n = 1.06 E = 137.99 }
1867
1868 #C31 : T-C4H9 + HO2 -> T-C4H9O + OH { A = 7.00E+12 n = .00 E = -4.18 }
1869 #C32 : T-C4H9 + CH3O2 -> T-C4H9O + CH3O { A = 7.00E+12 n = .00 E = -4.18 }
1870
1871 # Reactions of T-C4H9O
1872
1873 #C33 : T-C4H9O -> I-C3H7 + HCO + H { A = 1.78E+39 n = -7.30 E = 156.05 }
1874 #C34 : T-C4H9O -> I-C3H7 + CH2O { A = 7.25E+39 n = -7.59 E = 140.03 }
1875 #C35 : T-C4H9O -> CH3COCH3 + CH3 { A = 3.09E+13 n = 0.03 E = 58.87 }
1876
1877 # Reactions of T-C4H8
1878 # (not lumped)
1879
1880 IC36 : T-C4H8 -> T-C3H5 + CH3 { A = 1.92E+66 n =-14.22 E = 535.97 }
1881 IC37 : T-C4H8 + H -> C3H6 + CH3 { A = 5.68E+33 n = -5.72 E = 83.68 }
1882
1883 IC38 : T-C4H8 + H -> T-C4H7 + H2 { A = 3.40E+05 n = 2.50 E = 10.43 }
1884 IC39 : T-C4H8 + O -> T-C4H7 + OH { A = 1.21E+11 n = 0.70 E = 31.94 }
1885 IC40 : T-C4H8 + OH -> T-C4H7 + H2O { A = 5.20E+06 n = 2.00 E = -1.25 }
1886 IC41 : T-C4H8 + CH3 -> T-C4H7 + CH4 { A = 4.42E+00 n = 3.50 E = 23.74 }
1887 IC42 : T-C4H8 + HO2 -> T-C4H7 + H2O2 { A = 1.93E+04 n = 2.60 E = 58.20 }
1888
1889 #C43 : T-C4H8 + O -> I-C3H7 + HCO { A = 1.58E+07 n = 1.76 E = -5.09 }
1890 #C44 : T-C4H8 + O -> CH2CO + 2 CH3 { A = 3.33E+07 n = 1.76 E = 0.32 }
1891
1892 # Reactions of T-C4H7
1893 # (not lumped)
1894
1895 IC45 : T-C4H7 -> A-C3H4 + CH3 { A = 1.23E+47 n = -9.74 E = 310.70 }
1896
1897 #C46 : T-C4H7 + O -> I-C3H5CHO + H { A = 6.03E+13 n = .00 E = .00 }
1898 #C47 : T-C4H7 + O2 -> I-C3H5CHO + OH { A = 2.47E+13 n = -0.45 E = 96.32 }
1899 #C48 : T-C4H7 + O2 -> CH2CO + CH2O + CH3 { A = 7.14E+15 n = -1.21 E = 88.07 }
1900 #C49 : T-C4H7 + O2 -> A-C3H4 + CH2O + OH { A = 7.29E+29 n = -5.71 E = 89.75 }
1901 #C50 : T-C4H7 + HO2 -> T-C4H7O + OH { A = 7.00E+12 n = .00 E = -4.18 }
1902
1903 # Reactions of T-C4H7O
1904 # (not lumped)
1905
1906 #C51 : T-C4H7O -> I-C3H5CHO + H { A = 5.00E+13 n = .00 E = 121.75 }
1907 #C52 : T-C4H7O -> T-C3H5 + CH2O { A = 2.93E+21 n = -2.39 E = 148.91 }
1908 #C53 : T-C4H7O + O2 -> I-C3H5CHO + HO2 { A = 3.00E+10 n = .00 E = 6.90 }
1909
1910 # Reactions of I-C3H5CHO
1911 # (not lumped)
1912
1913 #C54 : I-C3H5CHO -> T-C3H5 + HCO { A = 3.05E+23 n = -2.37 E = 415.22 }
1914
1915 #C55 : I-C3H5CHO + H -> T-C3H5 + CO + H2 { A = 2.60E+12 n = .00 E = 10.88 }
1916 #C56 : I-C3H5CHO + O -> T-C3H5 + CO + OH { A = 7.18E+12 n = .00 E = 5.81 }
1917 #C57 : I-C3H5CHO + OH -> T-C3H5 + CO + H2O { A = 2.69E+10 n = 0.76 E = -1.42 }
1918 #C58 : I-C3H5CHO + CH3 -> T-C3H5 + CO + CH4 { A = 3.98E+12 n = .00 E = 36.40 }
1919 #C59 : I-C3H5CHO + HO2 -> T-C3H5 + CO + H2O2 { A = 1.00E+12 n = .00 E = 49.87 }
1920
1921 # Reactions of CH3COCH3
1922 # Revised from LLNL-NC16
1923 # (not lumped)
1924
1925 IC60 : CH3COCH3 -> 2 CH3 + CO { A = 1.22E+23 n = -1.99 E = 351.25 }
1926
1927 IC61 : CH3COCH3 + H -> CH2CO + CH3 + H2 { A = 2.30E+05 n = 2.72 E = 26.19 }
1928 IC62 : CH3COCH3 + O -> CH2CO + CH3 + OH { A = 5.13E+11 n = 0.21 E = 20.46 }
1929 IC63 : CH3COCH3 + OH -> CH2CO + CH3 + H2O { A = 3.38E+07 n = 1.74 E = 3.47 }
1930 IC64 : CH3COCH3 + O2 -> CH2CO + CH3 + HO2 { A = 6.03E+13 n = .00 E = 202.92 }
1931 IC65 : CH3COCH3 + CH3 -> CH2CO + CH3 + CH4 { A = 3.96E+11 n = .00 E = 40.94 }
1932 IC66 : CH3COCH3 + HO2 -> CH2CO + CH3 + H2O2 { A = 1.70E+13 n = .00 E = 85.61 }
1933
1934
1935
1936 #==========================================================================#
1937 # #
1938 # Zhong & Bozzelli, Int. J. Chem. Kinet., 1997, 29, 893-913 #
1939 # Zhong & Bozzelli, J. Phys. Chem. A, 1998, 102, 3537-3555 #
1940 # Robinson & Lindstedt, Comb. Flame, 2011, 158, 666-686 #
1941 # #
1942 #==========================================================================#
1943
1944
1945 # Cyclopentadiene
1946 # ---------------
1947
1948 # Robinson & Lindstedt 2011
1949 CP01f: C5H6 -> C5H5 + H { A = 3.24E+49 n =-10.01 E = 423.40 }
1950 CP02f: C5H6 + H -> C5H5 + H2 { A = 8.59E+07 n = 1.85 E = 13.97 }
1951
1952 CP03f: C5H6 + H -> A-C3H5 + C2H2 { A = 7.74E+36 n = -6.81 E = 137.60 }
1953
1954 CP04f: C5H6 + O -> C5H5 + OH { A = 4.77E+04 n = 2.71 E = 4.63 }
1955 CP05f: C5H6 + OH -> C5H5 + H2O { A = 3.08E+06 n = 2.00 E = .00 }
1956 CP06f: C5H6 + O2 -> C5H5 + HO2 { A = 1.00E+14 n = .00 E = 155.44 }
1957 CP07f: C5H6 + HO2 -> C5H5 + H2O2 { A = 1.10E+04 n = 2.60 E = 53.97 }
1958 CP08f: C5H6 + CH3 -> C5H5 + CH4 { A = 1.80E-01 n = 4.00 E = .00 }
1959
1960 # From CH4 + ?? (x0.5)
1961 CP09f: C5H6 + C2H3 -> C5H5 + C2H4 { A = 5.55E+04 n = 2.02 E = 13.17 }
1962 CP10f: C5H6 + A-C3H5 -> C5H5 + C3H6 { A = 2.15E+01 n = 3.31 E = 106.79 }
1963 CP11f: C5H6 + N-C4H5 -> C5H5 + C4H6 { A = 7.30E+10 n = 0.76 E = 63.51 }
1964
1965
1966 # Cyclopentadienyl radical
1967 # ------------------------
1968
1969 # Moskaleva & Lin 2000
1970 # Knyazev & Slagle 2002
1971 CP16f: C3H3 + C2H2 -> C5H5 { A = 6.87E+55 n =-12.50 E = 175.80 }
1972
1973 # Melius, Colvin, Marinov, Pitz, & Senkan 1996
1974 # Sharma & Green 2009 - Rate fitted at P=1bar
1975 # PRODUCTS TO BE CHECKED - Should be benzene?
1976 CP17 : C5H5 + CH3 -> C5H4CH2 + 2H { A = 4.91E+31 n = -4.85 E = 103.65 }
1977
1978 # Murakami et al. 2003 - Total rate
1979 # Kislov & Mebel - Branching ratio
1980 CP18 : C5H5 + C5H5 -> A2-C10H8 + 2H { A = 6.39E+29 n = -4.03 E = 147.30 }
1981
1982 # Robinson & Lindstedt 2011
1983 # estimated
1984 CP19f: C5H5 + C5H5 -> C9H7 + CH3 { A = 2.50E+12 n = .00 E = 40.00 }
1985
1986 # Kislov & Mebel 2008 - Full entrance rate
1987 CP20 : C5H5 + C5H6 -> C9H8 + CH3 { A = 7.86E-01 n = 3.07 E = 23.97 }
1988
1989 # Robinson & Lindstedt 2011
1990 CP21f: C5H5 + O -> N-C4H5 + CO { A = 1.27E+14 n = 0.26 E = 16.50 }
1991 CP22f: C5H5 + OH -> C4H6 + CO { A = 8.53E+13 n = 0.25 E = 18.20 }
1992 CP23f: C5H5 + OH -> C5H5O + H { A = 1.11E+05 n = 1.90 E = 138.60 }
1993 CP24f: C5H5 + O2 -> C5H4O + OH { A = 9.11E+15 n = -2.21 E = 10.20 }
1994 CP25f: C5H5 + O2 -> C5H5O + O { A = 4.37E+03 n = 2.40 E = 211.50 }
1995 CP26f: C5H5 + HO2 -> C5H5O + OH { A = 6.86E+13 n = 0.25 E = 21.30 }
1996
1997
1998 # Cyclopentadienoxy radical
1999 # -------------------------
2000
2001 # Robinson & Lindstedt 2011
2002 CP27 : C5H5O -> C5H4O + H { A = 8.18E+16 n = -2.32 E = 36.50 }
2003 CP28 : C5H5O -> N-C4H5 + CO { A = 2.15E+64 n =-15.14 E = 278.00 }
2004
2005 # 1/3 rate from CH3O
2006 CP29f: C5H5O + H -> C5H4O + H2 { A = 6.67E+12 n = .00 E = .00 }
2007 CP30f: C5H5O + O -> C5H4O + OH { A = 3.33E+12 n = .00 E = .00 }
2008 CP31f: C5H5O + OH -> C5H4O + H2O { A = 1.67E+12 n = .00 E = .00 }
2009 CP32f: C5H5O + O2 -> C5H4O + HO2 { A = 7.22E+09 n = .00 E = 7.32 }
2010
2011
2012 # Cyclopentadienone
2013 # -----------------
2014
2015 # Wang & Brezinsky 1998
2016 # Ristori et al. 2001
2017 # (products guessed)
2018 CP33 : C5H4O -> 2 C2H2 + CO { A = 6.20E+41 n = -7.87 E = 413.00 }
2019 CP34 : C5H4O -> C4H4 + CO { A = 5.00E+11 n = .00 E = 221.80 }
2020
2021 # From C2H4+R, C3H6+H
2022 # (products guessed)
2023 CP35 : C5H4O + H -> C2H3 + C2H2 + CO { A = 2.67E+12 n = 0.47 E = 22.72 }
2024 CP36 : C5H4O + O -> C3H3 + HCO + CO { A = 1.02E+08 n = 1.66 E = 2.75 }
2025
2026
2027
2028 #==========================================================================#
2029 # #
2030 # "Detailed kinetic modeling of benzene and toluene oxidation #
2031 # at high temperatures" #
2032 # Zoran M. Djurisic - Master's Thesis #
2033 # http://diesel.me.berkeley.edu/~zoran/publications/2000_MS_Thesis/ #
2034 # #
2035 #==========================================================================#
2036
2037
2038 # Benzene
2039 # -------
2040
2041 # Miller & Klippenstein 2003 (1bar)
2042 # Updated to include HPL from Harding et al. 2005
2043 BN00f: A1-C6H6 -> A1--C6H5 + H { A = 1.29E+61 n =-12.48 E = 619.59 }
2044
2045 # Mebel & Lin 1997
2046 BN01f: A1-C6H6 + H -> A1--C6H5 + H2 { A = 6.02E+08 n = 1.80 E = 68.42 }
2047
2048 # Lindsted & Skevis 1994
2049 BN02f: A1-C6H6 + O -> A1--C6H5 + OH { A = 2.00E+13 n = .00 E = 61.50 }
2050
2051 # Seta, Nakajima & Miyoshi 2006
2052 BN03f: A1-C6H6 + OH -> A1--C6H5 + H2O { A = 2.34E+04 n = 2.68 E = 3.07 }
2053 BN04f: A1-C6H6 + OH -> A1OH-C6H6O + H { A = 1.32E+02 n = 3.25 E = 23.39 }
2054
2055 # From C2H4 + O2 (x1.5)
2056 # Hua, Ruscic, Wang 2005
2057 # Backward ~ 2e12
2058 BN05f: A1-C6H6 + O2 -> A1--C6H5 + HO2 { A = 4.34E+14 n = .00 E = 269.00 }
2059
2060 # Taatjes, Wang, et al. 2010
2061 # Refitted
2062 BN06f: A1-C6H6 + O -> A1O-C6H5O + H { A = 1.99E+07 n = 1.80 E = 16.63 }
2063 BN07f: A1-C6H6 + O -> A1OH-C6H6O { A = 1.53E+10 n = 0.92 E = 13.79 }
2064 BN08f: A1-C6H6 + O -> C5H6 + CO { A = 1.53E+17 n = -0.89 E = 64.89 }
2065
2066
2067 # Phenyl radical
2068 # --------------
2069
2070 # Wang et al. 2000
2071 BN09f: A1--C6H5 + M9 -> O-C6H4 + H + M9 { A = 1.00E+84 n =-18.87 E = 376.98
2072 Ai= 4.30E+12 ni= 0.62 Ei= 323.43
2073 fcA = 0.098 fctA = 696
2074 fcb = 0.902 fctb = 358
2075 fcc = 1.0 fctc = 3856 }
2076
2077 # da Silva, Chen & Bozzelli 2007
2078 # From 3/4-methylphenyl + O2
2079 BN10f: A1--C6H5 + O2 -> A1O-C6H5O + O { A = 8.57E+20 n = -2.27 E = 30.08 }
2080
2081 # Frank, Herzler, Just & Wahl 1994
2082 BN11f: A1--C6H5 + O2 -> OC6H4O + H { A = 3.00E+13 n = .00 E = 37.58 }
2083 BN12f: A1--C6H5 + O -> A1O-C6H5O { A = 1.00E+14 n = .00 E = .00 }
2084
2085 BN13f: A1--C6H5 + OH -> A1O-C6H5O + H { A = 3.00E+13 n = .00 E = .00 }
2086 BN14f: A1--C6H5 + HO2 -> A1O-C6H5O + OH { A = 3.00E+13 n = .00 E = .00 }
2087
2088 # Tokmakov & Lin 1999/2002
2089 BN15f: A1--C6H5 + CH4 -> A1-C6H6 + CH3 { A = 3.89E-03 n = 4.57 E = 22.00 }
2090
2091
2092 # Phenol
2093 # ------
2094
2095 # Xu & Lin 2006
2096 # Rates for 1 atm
2097 # Formation of CO x0.765 to better match Horn & Roy 1989
2098 BN16f: A1OH-C6H6O -> C5H6 + CO { A = 6.59E+15 n = -0.61 E = 310.11 }
2099 BN17f: A1OH-C6H6O -> A1O-C6H5O + H { A = 1.01E+71 n =-15.92 E = 522.12 }
2100
2101 # From CH3OH+R
2102 BN18f: A1OH-C6H6O + H -> A1O-C6H5O + H2 { A = 4.20E+06 n = 2.10 E = 20.38 }
2103 BN19f: A1OH-C6H6O + OH -> A1O-C6H5O + H2O { A = 6.30E+06 n = 2.00 E = 6.28 }
2104 BN20f: A1OH-C6H6O + CH3 -> A1O-C6H5O + CH4 { A = 1.00E+07 n = 1.50 E = 41.59 }
2105
2106 # Brezinsky et al. 1998
2107 #N21f: A1OH-C6H6O + O2 -> A1O-C6H5O + HO2 { A = 7.32E+13 n = .00 E = 173.22 }
2108
2109
2110 # Phenoxy radical
2111 # 2-B1 state for O=C6H5
2112 # ---------------------
2113
2114 # Murakami et al. 2003
2115 BN22f: A1O-C6H5O -> C5H5 + CO { A = 2.90E+10 n = .00 E = 152.40 }
2116
2117 # From C2H5 + O (x2)
2118 BN23f: A1O-C6H5O + O -> OC6H4O + H { A = 6.34E+13 n = 0.03 E = -1.65 }
2119
2120 # From A-C3H5 + O2 - Total rate (x3/2)
2121 BN24f: A1O-C6H5O + O2 -> OC6H4O + OH { A = 6.51E+07 n = 1.30 E = 73.92 }
2122
2123
2124 # p-Benzoquinone
2125 # Thermoprop & Reactions for para
2126 # -------------------------------
2127
2128 BN25 : OC6H4O -> C5H4O + CO { A = 7.40E+11 n = .00 E = 246.86 }
2129
2130 BN26 : OC6H4O + H -> C5H5O + CO { A = 4.30E+09 n = 1.45 E = 16.18 }
2131 BN27 : OC6H4O + O -> CH2CO + C2H2 + 2 CO { A = 3.00E+13 n = .00 E = 20.92 }
2132
2133
2134 # Benzyne
2135 # -------
2136
2137 # Wang, Laskin, Moriarty, Frenklach 2000
2138 BN28 : O-C6H4 -> C4H2 + C2H2 { A = 1.20E+18 n = -0.34 E = 367.48 }
2139
2140 # Wang & Frenklach 1997
2141 BN29f: N-C4H3 + C2H2 -> O-C6H4 + H { A = 6.90E+46 n =-10.01 E = 125.94 }
2142
2143 BN30 : O-C6H4 + OH -> C5H5 + CO { A = 1.00E+13 n = .00 E = .00 }
2144
2145
2146
2147 #==========================================================================#
2148 # #
2149 # Toluene chemistry #
2150 # #
2151 # Oehlschlaeger, Davidson & Hanson, Comb. Flame, 2006, 147, 195-208 #
2152 # #
2153 #==========================================================================#
2154
2155
2156 # Toluene / Benzyl decomposition
2157 # ------------------------------
2158
2159 # Tokmakov et al. 2001 (x1.2 to match exp.)
2160 # Sheen, Rosado-Reyes, Tsang 2013 (within 2%)
2161 T01f: A1CH3-C7H8 + H -> A1-C6H6 + CH3 { A = 2.31E+06 n = 2.17 E = 17.42 }
2162
2163 # Klippenstein et al. 2007
2164 # Almost indep or pressure => HPL
2165 T02f: A1CH3-C7H8 -> A1CH2-C7H7 + H { A = 1.56E+13 n = 0.68 E = 373.24 }
2166 T03f: A1CH3-C7H8 -> A1--C6H5 + CH3 { A = 4.35E+22 n = -1.73 E = 436.01 }
2167 # P=1bar - 1000K-2500K
2168 T04f: A1CH2-C7H7 + H -> A1--C6H5 + CH3 { A = 5.83E+67 n =-14.15 E = 285.89 }
2169
2170 # Assumed products. Other choices: C7H6 + H, c-C7H7
2171 # Rate from Oehlschlaeger et al. 2006 (1.5 atm)
2172 T05f: A1CH2-C7H7 -> C5H5 + C2H2 { A = 8.20E+14 n = .00 E = 337.55 }
2173
2174
2175 # Toluene
2176 # -------
2177
2178 # Oehlschlaeger et al. 2006 (1.5 atm)
2179 T06f: A1CH3-C7H8 + H -> A1CH2-C7H7 + H2 { A = 6.47E+00 n = 3.98 E = 14.16 }
2180
2181 # From C3H8+O (x0.5)
2182 T07f: A1CH3-C7H8 + O -> A1CH2-C7H7 + OH { A = 9.50E+04 n = 2.68 E = 15.55 }
2183
2184 # From A1+O (x5/6)
2185 T08f: A1CH3-C7H8 + O -> OA1CH3-C7H7O + H { A = 1.66E+07 n = 1.80 E = 16.63 }
2186 T09f: A1CH3-C7H8 + O -> HOA1CH3-C7H8O { A = 1.28E+10 n = 0.92 E = 13.79 }
2187
2188 # Seta, Nakajima & Miyoshi 2006
2189 # Better match with Vasudevan, Davidson & Hanson 2005
2190 T10f: A1CH3-C7H8 + OH -> A1CH2-C7H7 + H2O { A = 1.77E+05 n = 2.39 E = -2.52 }
2191 T11f: A1CH3-C7H8 + OH -> A1OH-C6H6O + CH3 { A = 7.83E+02 n = 2.88 E = 13.48 }
2192 T12f: A1CH3-C7H8 + OH -> HOA1CH3-C7H8O + H { A = 3.14E+01 n = 3.37 E = 19.75 }
2193
2194 # Oehlschlaeger et al. 2006 (1.5 atm)
2195 T13f: A1CH3-C7H8 + O2 -> A1CH2-C7H7 + HO2 { A = 2.18E+07 n = 2.50 E = 192.65 }
2196
2197 # Baulch et al. 2005
2198 T14f: A1CH3-C7H8 + HO2 -> A1CH2-C7H7 + H2O2 { A = 9.33E+04 n = 2.50 E = 61.44 }
2199
2200 # From C3H8+CH3 (x0.5)
2201 T15f: A1CH3-C7H8 + CH3 -> A1CH2-C7H7 + CH4 { A = 4.52E-01 n = 3.65 E = 29.93 }
2202
2203 # Heckmann, Hippler & Troe 1996
2204 T16f: A1CH3-C7H8 + A1--C6H5 -> A1CH2-C7H7 + A1-C6H6 { A = 7.94E+13 n = .00 E = 50.00 }
2205
2206
2207 # Benzyl radical
2208 # --------------
2209
2210 # da Silva & Bozzelli 2012 - P=1atm
2211 T17f: A1CH2-C7H7 + O -> A1-C6H6 + HCO { A = 6.98E+12 n = 0.33 E = 2.87 }
2212 T18f: A1CH2-C7H7 + O -> A1CHO-C7H6O + H { A = 2.75E+13 n = 0.07 E = 3.06 }
2213
2214 # Murakami et al. 2007 - HPL
2215 # Canneaux et al. 2008 - Benzylperoxy isomerization
2216 # Benzylperoxy in Steady State
2217 T19f: A1CH2-C7H7 + O2 -> A1CHO-C7H6O + OH { A = 3.76E+15 n = -1.55 E = 47.37 }
2218
2219 # da Silva & Bozzelli 2008
2220 T21f: A1CH2-C7H7 + HO2 -> A1CH2O-C7H7O + OH { A = 1.19E+09 n = 1.03 E = -9.41 }
2221
2222 # From A-C3H5
2223 T22 : A1CH2-C7H7 + C3H3 -> A2-C10H8 + 2H { A = 1.88E+38 n = -7.53 E = 99.91 }
2224
2225
2226 # Alcoxy Benzyl
2227 # -------------
2228
2229 # Choi, Xia, Park & Lin 2000
2230 T23f: A1--C6H5 + CH2O -> A1-C6H6 + HCO { A = 8.55E+04 n = 2.19 E = 0.16 }
2231
2232 # Xia & Lin 2000
2233 T24f: A1CH2O-C7H7O -> A1CHO-C7H6O + H { A = 1.27E+13 n = .00 E = 86.19 }
2234
2235 # da Silva & Bozzelli 2009 - P=1atm
2236 T25f: A1CH2O-C7H7O -> A1--C6H5 + CH2O { A = 7.21E+33 n = -6.21 E = 154.18 }
2237 T26f: A1CH2O-C7H7O -> A1-C6H6 + HCO { A = 2.37E+32 n = -6.10 E = 120.54 }
2238
2239 # From CH3O (x2/3)
2240 T27f: A1CH2O-C7H7O + H -> A1CHO-C7H6O + H2 { A = 1.33E+13 n = .00 E = .00 }
2241 T28f: A1CH2O-C7H7O + O -> A1CHO-C7H6O + OH { A = 6.67E+12 n = .00 E = .00 }
2242 T29f: A1CH2O-C7H7O + OH -> A1CHO-C7H6O + H2O { A = 3.33E+12 n = .00 E = .00 }
2243 T30f: A1CH2O-C7H7O + O2 -> A1CHO-C7H6O + HO2 { A = 4.11E+10 n = .00 E = 7.32 }
2244
2245
2246 # Benzaldehyde
2247 # ------------
2248
2249 # From CH3CHO - Baulch et al. 2005
2250 # Grela & Colussi 1986 - Loss of H then loss of CO
2251 T31 : A1CHO-C7H6O -> A1--C6H5 + CO + H { A = 2.10E+16 n = .00 E = 342.00 }
2252
2253 # From CH3CHO
2254 T32 : A1CHO-C7H6O + H -> A1--C6H5 + CO + H2 { A = 2.05E+09 n = 1.16 E = 10.06 }
2255 T33 : A1CHO-C7H6O + O -> A1--C6H5 + CO + OH { A = 2.92E+12 n = .00 E = 7.57 }
2256 T34 : A1CHO-C7H6O + OH -> A1--C6H5 + CO + H2O { A = 2.34E+10 n = .73 E = -4.66 }
2257 T35 : A1CHO-C7H6O + CH3 -> A1--C6H5 + CO + CH4 { A = 2.72E+06 n = 1.77 E = 24.77 }
2258
2259
2260 # Cresol
2261 # All isomers lumped into meta
2262 # ----------------------------
2263
2264 # From A1OH/A1O
2265 T36f: HOA1CH3-C7H8O -> OA1CH3-C7H7O + H { A = 1.01E+71 n =-15.92 E = 522.12 }
2266 T37f: HOA1CH3-C7H8O + H -> OA1CH3-C7H7O + H2 { A = 4.20E+06 n = 2.10 E = 20.38 }
2267 T38f: HOA1CH3-C7H8O + O -> OA1CH3-C7H7O + OH { A = 1.30E+05 n = 2.50 E = 20.92 }
2268 T39f: HOA1CH3-C7H8O + OH -> OA1CH3-C7H7O + H2O { A = 6.30E+06 n = 2.00 E = 6.28 }
2269 T40f: HOA1CH3-C7H8O + CH3-> OA1CH3-C7H7O + CH4 { A = 1.00E+07 n = 1.50 E = 41.59 }
2270
2271 T41 : OA1CH3-C7H7O -> C5H4CH2 + CO + H { A = 2.90E+10 n = .00 E = 152.40 }
2272
2273
2274 # Methyl-phenyl
2275 # All isomers lumped into meta
2276 # ----------------------------
2277
2278 # From A1 (x0.65)
2279 # From symmetry should be x5/6
2280 # Seta, Nakajima & Miyoshi 2006 - Rate for OH - Same as A1 x0.65
2281 T42f: A1CH3-C7H8 -> A1CH3*-C7H7 + H { A = 8.39E+60 n =-12.48 E = 619.59 }
2282 T43f: A1CH3-C7H8 + H -> A1CH3*-C7H7 + H2 { A = 3.91E+08 n = 1.80 E = 68.42 }
2283 T44f: A1CH3-C7H8 + O -> A1CH3*-C7H7 + OH { A = 1.60E+13 n = .00 E = 61.50 }
2284 T45f: A1CH3-C7H8 + OH -> A1CH3*-C7H7 + H2O { A = 1.36E+04 n = 2.69 E = 2.59 }
2285 T46f: A1CH3-C7H8 + CH3 -> A1CH3*-C7H7 + CH4 { A = 1.79E-02 n = 4.46 E = 57.06 }
2286
2287 # From A1-
2288 T47f: A1CH3*-C7H7 + O -> OA1CH3-C7H7O { A = 1.00E+14 n = .00 E = .00 }
2289 T48f: A1CH3*-C7H7 + OH -> OA1CH3-C7H7O + H { A = 3.00E+13 n = .00 E = .00 }
2290 T49f: A1CH3*-C7H7 + HO2 -> OA1CH3-C7H7O + OH { A = 3.00E+13 n = .00 E = .00 }
2291
2292 # da Silva, Chen & Bozzelli 2007
2293 # Assumed products for methyloxepinoxy decomposition
2294 T50f: A1CH3*-C7H7 + O2 -> OA1CH3-C7H7O + O { A = 8.57E+20 n = -2.27 E = 30.08 }
2295 T51 : A1CH3*-C7H7 + O2 -> C5H4CH2 + CO2 + H { A = 2.55E+13 n = -0.44 E = -6.90 }
2296 T52 : A1CH3*-C7H7 + O2 -> P-C3H4 + C2H3 + 2CO { A = 2.55E+13 n = -0.44 E = -6.90 }
2297
2298
2299
2300 #===============================================================================#
2301 # #
2302 # Styrene Chemistry #
2303 # Adapted from C2H4 chemistry #
2304 # Additional rates from Kislov & Mebel 2005 #
2305 # #
2306 #===============================================================================#
2307
2308
2309 # Styrene
2310 # -------
2311
2312 # Greda et al. 1992
2313 ST01 : A1C2H3-C8H8 -> A1-C6H6 + H2C2 { A = 2.40E+14 n = .00 E = 326.90 }
2314
2315 # Wang & Frenklach 1997 - estimated HPL
2316 ST02f: A1--C6H5 + C2H3 -> A1C2H3-C8H8 { A = 6.00E+12 n = .00 E = .00 }
2317
2318 # Tokmakov & Lin 2004
2319 ST03f: A1--C6H5 + C2H4 -> A1C2H3-C8H8 + H { A = 3.62E+28 n = -4.24 E = 99.85 }
2320 ST04f: A1C2H3-C8H8 + H -> A1-C6H6 + C2H3 { A = 5.62E+24 n = -3.00 E = 82.97 }
2321
2322 # From A1CH3
2323 ST05f: A1C2H3-C8H8 + OH -> A1OH-C6H6O + C2H3 { A = 7.83E+02 n = 2.88 E = 13.48 }
2324
2325 # From C2H4 (x0.5)
2326 ST06f: A1C2H3-C8H8 -> A1C2H2-C8H7 + H { A = 3.01E+14 n = 0.34 E = 465.49 }
2327 ST07f: A1C2H3-C8H8 + H -> A1C2H2-C8H7 + H2 { A = 6.35E+04 n = 2.75 E = 48.74 }
2328 ST08f: A1C2H3-C8H8 + OH -> A1C2H2-C8H7 + H2O { A = 1.12E+04 n = 2.75 E = 9.27 }
2329
2330 # From A1 (x1/3)
2331 ST09f: A1C2H3-C8H8 -> A1C2H3*-C8H7 + H { A = 4.30E+60 n =-12.48 E = 619.59 }
2332 ST10f: A1C2H3-C8H8 + H -> A1C2H3*-C8H7 + H2 { A = 2.01E+08 n = 1.80 E = 68.42 }
2333 ST11f: A1C2H3-C8H8 + OH -> A1C2H3*-C8H7 + H2O { A = 7.80E+03 n = 2.68 E = 3.07 }
2334
2335 # From C2H4 (x0.5)
2336 # Half for each carbon atoms
2337 ST12f: A1C2H3-C8H8 + O -> A1CH2-C7H7 + HCO { A = 1.95E+08 n = 1.36 E = 3.71 }
2338 ST13f: A1C2H3-C8H8 + O -> A1CHO-C7H6O + T-CH2 { A = 3.58E+04 n = 2.47 E = 3.89 }
2339
2340
2341 # Styryl radical
2342 # --------------
2343
2344 # Tolkmakov & Lin 2003
2345 ST16f: A1--C6H5 + C2H2 -> A1C2H-C8H6 + H { A = 2.66E+32 n = -5.30 E = 99.52 }
2346 ST17f: A1--C6H5 + C2H2 -> A1C2H2-C8H7 { A = 4.80E+44 n = -9.90 E = 73.75 }
2347
2348 # Kislov & Mebel 2005 - HPL
2349 ST18f: A1C2H2-C8H7 -> A1C2H3*-C8H7 { A = 5.90E+10 n = 0.55 E = 115.34 }
2350
2351 # From N-C4H5
2352 ST19f: A1C2H2-C8H7 -> A1C2H-C8H6 + H { A = 1.81E+54 n =-12.69 E = 215.02 }
2353 ST20f: A1C2H2-C8H7 + H -> A1C2H-C8H6 + H2 { A = 1.50E+13 n = .00 E = .00 }
2354 ST21f: A1C2H2-C8H7 + OH -> A1C2H-C8H6 + H2O { A = 2.50E+12 n = .00 E = .00 }
2355 ST22f: A1C2H2-C8H7 + O2 -> A1C2H-C8H6 + HO2 { A = 6.70E+05 n = 1.61 E = -1.61 }
2356
2357 # From C2H3 + O
2358 ST23f: A1C2H2-C8H7 + O -> A1CH2-C7H7 + CO { A = 1.03E+13 n = 0.21 E = -1.79 }
2359
2360 # From C2H3 + O2
2361 ST24 : A1C2H2-C8H7 + O2 -> A1CH2-C7H7 + CO + O { A = 3.03E+11 n = 0.29 E = 0.05 }
2362 ST25f: A1C2H2-C8H7 + O2 -> A1CHO-C7H6O + HCO { A = 4.58E+16 n = -1.39 E = 4.25 }
2363
2364
2365 # Ethynylbenzene
2366 # --------------
2367
2368 # Goulay & Leone 2006
2369 # Woon, Park & Jin-Young 2009
2370 ST26f: A1-C6H6 + C2H -> A1C2H-C8H6 + H { A = 2.00E+14 n = .00 E = .00 }
2371
2372 # From A1 (x1/3)
2373 ST27f: A1C2H-C8H6 -> A1C2H*-C8H5 + H { A = 4.30E+60 n =-12.48 E = 619.59 }
2374 ST28f: A1C2H-C8H6 + H -> A1C2H*-C8H5 + H2 { A = 2.01E+08 n = 1.80 E = 68.42 }
2375 ST29f: A1C2H-C8H6 + OH -> A1C2H*-C8H5 + H2O { A = 7.80E+03 n = 2.68 E = 3.07 }
2376
2377 # From C2H2
2378 ST30f: A1C2H-C8H6 + O -> A1--C6H5 + HCCO { A = 3.70E+09 n = 1.28 E = 10.34 }
2379
2380 ST31f: A1C2H-C8H6 + OH -> A1--C6H5 + CH2CO { A = 2.10E+01 n = 3.22 E = -1.76 }
2381 ST32f: A1C2H-C8H6 + OH -> A1CH2-C7H7 + CO { A = 6.40E+08 n = 0.73 E = 10.79 }
2382
2383
2384
2385 #==========================================================================#
2386 # #
2387 # Ethyl-Benzene chemistry #
2388 # #
2389 # Adapted from C3H8 and Toluene/Benzene chemistry #
2390 # #
2391 #==========================================================================#
2392
2393
2394 # Ethylbenzene
2395 # ------------
2396
2397 # Estimated from C3H7+H - HPL
2398 EB01f: A1C2H4-C8H9 + H -> A1C2H5-C8H10 { A = 3.61E+13 n = .00 E = .00 }
2399
2400 # Estimated from C2H5+CH3 - HPL
2401 EB02f: A1CH2-C7H7 + CH3 -> A1C2H5-C8H10 { A = 2.00E+13 n = .00 E = .00 }
2402 EB03f: A1--C6H5 + C2H5 -> A1C2H5-C8H10 { A = 2.00E+13 n = .00 E = .00 }
2403
2404 # From A1CH3
2405 EB04f: A1C2H5-C8H10 + H -> A1-C6H6 + C2H5 { A = 2.31E+06 n = 2.17 E = 17.42 }
2406 EB05f: A1C2H5-C8H10 + OH -> A1OH-C6H6O + C2H5 { A = 7.83E+02 n = 2.88 E = 13.48 }
2407
2408 # From C3H8 (x0.5)
2409 EB06f: A1C2H5-C8H10 + H -> A1C2H4-C8H9 + H2 { A = 4.68E+07 n = 1.97 E = 34.31 }
2410 EB07f: A1C2H5-C8H10 + O -> A1C2H4-C8H9 + OH { A = 9.95E+04 n = 2.68 E = 15.55 }
2411 EB08f: A1C2H5-C8H10 + OH -> A1C2H4-C8H9 + H2O { A = 2.67E+03 n = 2.94 E = -1.75 }
2412 EB09f: A1C2H5-C8H10 + CH3 -> A1C2H4-C8H9 + CH4 { A = 4.52E-01 n = 3.65 E = 29.93 }
2413 EB10f: A1C2H5-C8H10 + HO2 -> A1C2H4-C8H9 + H2O2 { A = 2.38E+04 n = 2.55 E = 69.00 }
2414
2415
2416 # N-Ethylbenzene radical
2417 # ----------------------
2418
2419 # Tokmakov & Lin 2004
2420 # HPL for both decompositions
2421 EB11f: A1C2H4-C8H9 -> A1--C6H5 + C2H4 { A = 1.72E+11 n = 0.78 E = 161.94 }
2422 EB12f: A1C2H4-C8H9 -> A1C2H3-C8H8 + H { A = 3.79E+06 n = 1.99 E = 134.33 }
2423
2424 # From C3H7
2425 EB13f: A1C2H4-C8H9 + H -> A1C2H3-C8H8 + H2 { A = 1.80E+12 n = .00 E = .00 }
2426 EB14f: A1C2H4-C8H9 + OH -> A1C2H3-C8H8 + H2O { A = 2.41E+13 n = .00 E = .00 }
2427 EB15f: A1C2H4-C8H9 + O2 -> A1C2H3-C8H8 + HO2 { A = 3.70E+16 n = -1.63 E = 14.30 }
2428 EB16f: A1C2H4-C8H9 + CH3 -> A1C2H3-C8H8 + CH4 { A = 3.31E+12 n = .00 E = -3.22 }
2429
2430 EB17f: A1C2H4-C8H9 + O -> A1CH2-C7H7 + CH2O { A = 9.60E+13 n = .00 E = .00 }
2431
2432 # From NC7
2433 EB18 : A1C2H4-C8H9 + HO2 -> A1CH2-C7H7 + CH2O + OH { A = 7.00E+12 n = .00 E = -4.18 }
2434 EB19 : A1C2H4-C8H9 + CH3O2 -> A1CH2-C7H7 + CH2O + CH3O { A = 7.00E+12 n = .00 E = -4.18 }
2435
2436
2437
2438 #=========================================================================#
2439 # #
2440 # Xylene Oxidation Chemistry #
2441 # Adapted from Toluene Chemistry #
2442 # #
2443 #=========================================================================#
2444
2445
2446 # Xylene
2447 # ------
2448
2449 # From A1CH3 (x2)
2450 XY01f: A1CH3CH3-C8H10 -> A1CH3CH2-C8H9 + H { A = 2.12E+13 n = 0.68 E = 373.24 }
2451 XY02f: A1CH3CH3-C8H10 -> A1CH3*-C7H7 + CH3 { A = 8.70E+22 n = -1.73 E = 436.01 }
2452
2453 # From A1CH3+R (x2)
2454 XY03f: A1CH3CH3-C8H10 + H -> A1CH3CH2-C8H9 + H2 { A = 1.29E+01 n = 3.98 E = 14.16 }
2455 XY04f: A1CH3CH3-C8H10 + O -> A1CH3CH2-C8H9 + OH { A = 1.90E+05 n = 2.68 E = 15.55 }
2456 XY05f: A1CH3CH3-C8H10 + OH -> A1CH3CH2-C8H9 + H2O { A = 3.54E+05 n = 2.39 E = -2.52 }
2457 XY06f: A1CH3CH3-C8H10 + O2 -> A1CH3CH2-C8H9 + HO2 { A = 4.36E+07 n = 2.50 E = 192.65 }
2458 XY07f: A1CH3CH3-C8H10 + HO2 -> A1CH3CH2-C8H9 + H2O2 { A = 1.87E+05 n = 2.50 E = 61.44 }
2459 XY08f: A1CH3CH3-C8H10 + CH3 -> A1CH3CH2-C8H9 + CH4 { A = 9.03E-01 n = 3.65 E = 29.93 }
2460
2461 # From A1CH3+X (x2)
2462 XY09f: A1CH3CH3-C8H10 + H -> A1CH3-C7H8 + CH3 { A = 4.62E+06 n = 2.17 E = 17.42 }
2463 XY10f: A1CH3CH3-C8H10 + OH -> HOA1CH3-C7H8O + CH3 { A = 1.57E+03 n = 2.88 E = 13.48 }
2464
2465 # !!!! CAREFUL !!!!
2466 # Path from Bounaceur et al. 2005
2467 # Rate from A1+O (x2/3)
2468 XY11 : A1CH3CH3-C8H10 + O -> A1CH3-C7H8 + CO + 2H { A = 1.82E+08 n = 1.55 E = 12.93 }
2469
2470
2471 # Xylyl radical
2472 # -------------
2473
2474 # Path from Bournaceur et al. 2005
2475 # Rate from A1CH2
2476 XY12 : A1CH3CH2-C8H9 -> A1-C6H6 + H + C2H2 { A = 8.20E+14 n = .00 E = 337.55 }
2477
2478 XY13f: A1CH3CH2-C8H9 + H -> A1CH3*-C7H7 + CH3 { A = 5.83E+67 n =-14.15 E = 285.89 }
2479
2480 # From A1CH2+O
2481 XY14f: A1CH3CH2-C8H9 + O -> A1CH3CHO-C8H8O + H { A = 2.75E+13 n = 0.07 E = 3.06 }
2482 XY15f: A1CH3CH2-C8H9 + O -> A1CH3-C7H8 + HCO { A = 6.98E+12 n = 0.33 E = 2.87 }
2483
2484 # From A1CH2+O2
2485 # Addition from Murakami et al. 2009
2486 # Peroxy isomerization from Canneaux et al. 2008
2487 XY16f: A1CH3CH2-C8H9 + O2 -> A1CH3CHO-C8H8O + OH { A = 1.38E+02 n = 2.42 E = 31.13 }
2488
2489 # From A1CH2+HO2
2490 # Assumed unique decomposition into A1CHO+H
2491 XY19 : A1CH3CH2-C8H9 + HO2 -> A1CH3CHO-C8H8O + H + OH { A = 1.19E+09 n = 1.03 E = -9.41 }
2492
2493 # From A-C3H5 + C3H3
2494 XY20 : A1CH3CH2-C8H9 + C3H3 -> A2CH3-C11H10 + 2H { A = 1.88E+38 n = -7.53 E = 99.91 }
2495
2496
2497 # Tolualdehyde
2498 # ------------
2499
2500 # From A1CH3 & A1CHO decomposition
2501 XY21f: A1CH3CHO-C8H8O -> A1CHOCH2-C8H7O + H { A = 1.56E+13 n = 0.68 E = 373.24 }
2502 XY22 : A1CH3CHO-C8H8O -> A1--C6H5 + CO + CH3 { A = 4.35E+22 n = -1.73 E = 436.01 }
2503 XY23 : A1CH3CHO-C8H8O -> A1CH3*-C7H7 + CO + H { A = 2.10E+16 n = .00 E = 342.00 }
2504
2505 # From A1CH3+R
2506 XY24f: A1CH3CHO-C8H8O + H -> A1CHOCH2-C8H7O + H2 { A = 6.47E+00 n = 3.98 E = 14.16 }
2507 XY25f: A1CH3CHO-C8H8O + O -> A1CHOCH2-C8H7O + OH { A = 9.50E+04 n = 2.68 E = 15.55 }
2508 XY26f: A1CH3CHO-C8H8O + OH -> A1CHOCH2-C8H7O + H2O { A = 1.77E+05 n = 2.39 E = -2.52 }
2509 XY27f: A1CH3CHO-C8H8O + CH3 -> A1CHOCH2-C8H7O + CH4 { A = 4.52E-01 n = 3.65 E = 29.93 }
2510
2511 # From A1CHO+R
2512 XY28 : A1CH3CHO-C8H8O + H -> A1CH3*-C7H7 + CO + H2 { A = 2.05E+09 n = 1.16 E = 10.06 }
2513 XY29 : A1CH3CHO-C8H8O + O -> A1CH3*-C7H7 + CO + OH { A = 2.92E+12 n = .00 E = 7.57 }
2514 XY30 : A1CH3CHO-C8H8O + OH -> A1CH3*-C7H7 + CO + H2O { A = 2.34E+10 n = 0.73 E = -4.66 }
2515 XY31 : A1CH3CHO-C8H8O + CH3 -> A1CH3*-C7H7 + CO + CH4 { A = 2.72E+06 n = 1.77 E = 24.77 }
2516
2517
2518 # Tolualdehyde radical
2519 # --------------------
2520
2521 # From A1CH2+O
2522 XY32f: A1CHOCH2-C8H7O + O -> A1CHOCHO-C8H6O2 + H { A = 2.75E+13 n = 0.07 E = 3.06 }
2523 XY33f: A1CHOCH2-C8H7O + O -> A1CHO-C7H6O + HCO { A = 6.98E+12 n = 0.33 E = 2.87 }
2524
2525 # From A1CH2+HO2
2526 # Assumed unique decomposition into A1CHO+H
2527 XY33 : A1CHOCH2-C8H7O + HO2 -> A1CHOCHO-C8H6O2 + H + OH { A = 1.19E+09 n = 1.03 E = -9.41 }
2528
2529
2530 # Phthalaldehyde
2531 # --------------
2532
2533 # From A1CHO decomposition (x2)
2534 XY34 : A1CHOCHO-C8H6O2 -> A1--C6H5 + 2 CO + H { A = 4.20E+16 n = .00 E = 342.00 }
2535
2536 # From A1CHO+R (x2)
2537 XY35 : A1CHOCHO-C8H6O2 + H -> A1CHO-C7H6O + CO + H { A = 4.10E+09 n = 1.16 E = 10.06 }
2538 XY36 : A1CHOCHO-C8H6O2 + O -> A1CHO-C7H6O + CO + O { A = 5.84E+12 n = .00 E = 7.57 }
2539 XY37 : A1CHOCHO-C8H6O2 + OH -> A1CHO-C7H6O + CO + OH { A = 4.68E+10 n = 0.73 E = -4.66 }
2540 XY38 : A1CHOCHO-C8H6O2 + CH3 -> A1CHO-C7H6O + CO + CH3 { A = 5.44E+06 n = 1.77 E = 24.77 }
2541
2542
2543
2544 #==========================================================================#
2545 # #
2546 # Indene chemistry #
2547 # Adapted from Cyclopentadiene #
2548 # #
2549 #==========================================================================#
2550
2551
2552 # Indene
2553 # ------
2554
2555 # Kislov & Mebel 2007
2556 # Rate estimated
2557 I00f: A1--C6H5 + C3H3 -> C9H8 { A = 1.00E+13 n = .00 E = .00 }
2558
2559 # Kislov & Mebel 2007
2560 I01f: A1CH2-C7H7 + C2H2 -> C9H8 + H { A = 3.16E+04 n = 2.48 E = 46.28 }
2561
2562 I02f: C9H8 -> C9H7 + H { A = 3.24E+49 n =-10.01 E = 423.40 }
2563 I03f: C9H8 + H -> C9H7 + H2 { A = 8.59E+07 n = 1.85 E = 13.97 }
2564
2565 I05f: C9H8 + O -> C9H7 + OH { A = 4.77E+04 n = 2.71 E = 4.63 }
2566 I06f: C9H8 + OH -> C9H7 + H2O { A = 3.08E+06 n = 2.00 E = .00 }
2567 I07f: C9H8 + O2 -> C9H7 + HO2 { A = 1.00E+14 n = .00 E = 155.44 }
2568 I08f: C9H8 + HO2 -> C9H7 + H2O2 { A = 1.10E+04 n = 2.60 E = 53.97 }
2569 I09f: C9H8 + CH3 -> C9H7 + CH4 { A = 1.80E-01 n = 4.00 E = .00 }
2570
2571 # From C2H4 + O
2572 #I10 : C9H8 + O -> O-C6H4 + C2H3 + CO + H { A = 1.02E+08 n = 1.66 E = 2.75 }
2573
2574
2575 # Indenyl radical
2576 # 2/5 of the rate for C5H5
2577 # ------------------------
2578
2579 I12 : C9H7 + C5H5 -> A3-C14H10 + 2H { A = 2.56E+29 n = -4.03 E = 147.30 }
2580 I13 : C9H7 + CH3 -> A2-C10H8 + 2H { A = 1.96E+31 n = -4.85 E = 103.65 }
2581
2582 # TEST - GB
2583 #I14 : C9H7 -> C5H5 + C4H2 { A = 1.00E+10 n= .00 E = 250.00 }
2584
2585 I15 : C9H7 + O -> A1C2H2-C8H7 + CO { A = 5.08E+13 n = 0.26 E = 16.50 }
2586 I16 : C9H7 + OH -> A1C2H3-C8H8 + CO { A = 3.41E+13 n = 0.25 E = 18.20 }
2587 I17 : C9H7 + OH -> C9H6O + 2H { A = 4.44E+04 n = 1.90 E = 138.60 }
2588 I18 : C9H7 + O2 -> C9H6O + OH { A = 3.64E+15 n = -2.21 E = 10.20 }
2589 I19 : C9H7 + O2 -> C9H6O + O + H { A = 1.75E+03 n = 2.40 E = 211.50 }
2590 I20 : C9H7 + HO2 -> C9H6O + OH + H { A = 2.74E+13 n = 0.25 E = 21.30 }
2591
2592 # From A-C3H5 + C3H3
2593 I21 : C9H7 + C3H3 -> A2R5-C12H8 + 2H { A = 1.88E+38 n = -7.53 E = 99.91 }
2594
2595
2596 # Indenone
2597 # --------
2598
2599 I22 : C9H6O -> O-C6H4 + C2H2 + CO { A = 6.20E+41 n = -7.87 E = 413.00 }
2600
2601 I23 : C9H6O + H -> A1C2H2-C8H7 + CO { A = 1.37E+09 n = 1.46 E = 5.67 }
2602 I24 : C9H6O + O -> O-C6H4 + CH2CO + CO { A = 1.02E+08 n = 1.66 E = 2.75 }
2603
2604
2605
2606 #==========================================================================#
2607 # #
2608 # Napthalene Oxidation Chemistry #
2609 # Adapted from Benzene #
2610 # #
2611 #==========================================================================#
2612
2613 # Naphthalene
2614 # 5/3 of the rate for A1
2615 # ----------------------
2616
2617 NP01f: A2-C10H8 -> A2--C10H7 + H { A = 8.60E+60 n =-12.48 E = 619.55 }
2618 NP02f: A2-C10H8 + H -> A2--C10H7 + H2 { A = 4.01E+08 n = 1.80 E = 68.42 }
2619 NP03f: A2-C10H8 + OH -> A2--C10H7 + H2O { A = 3.90E+04 n = 2.68 E = 3.07 }
2620
2621 NP04f: A2-C10H8 -> A2*-C10H7 + H { A = 8.60E+60 n =-12.48 E = 619.55 }
2622 NP05f: A2-C10H8 + H -> A2*-C10H7 + H2 { A = 4.01E+08 n = 1.80 E = 68.42 }
2623 NP06f: A2-C10H8 + OH -> A2*-C10H7 + H2O { A = 3.90E+04 n = 2.68 E = 3.07 }
2624
2625 NP07f: A2-C10H8 + O -> A2O-C10H7O + H { A = 3.32E+07 n = 1.80 E = 16.63 }
2626 NP08f: A2-C10H8 + O -> A2OH-C10H8O { A = 2.55E+10 n = 0.92 E = 13.79 }
2627 NP09f: A2-C10H8 + O -> C9H8 + CO { A = 2.55E+17 n = -0.89 E = 64.89 }
2628
2629 NP10f: A2-C10H8 + OH -> A2OH-C10H8O + H { A = 2.20E+02 n = 3.25 E = 23.39 }
2630
2631
2632 # Naphthyl radical
2633 # Full rate for A1-
2634 # -----------------
2635
2636 # Park, Nguyen, Xu, Lin 2009
2637 NP11f: A2--C10H7 -> A2*-C10H7 { A = 1.51E+07 n = .00 E = 184.85 }
2638
2639 NP12f: A2--C10H7 + O2 -> A2O-C10H7O + O { A = 8.57E+20 n = -2.27 E = 30.08 }
2640 NP13f: A2*-C10H7 + O2 -> A2O-C10H7O + O { A = 8.57E+20 n = -2.27 E = 30.08 }
2641
2642 NP14 : A2--C10H7 + O2 -> C9H6O + CO + H { A = 3.00E+13 n = .00 E = 37.58 }
2643 NP15 : A2*-C10H7 + O2 -> C9H6O + CO + H { A = 3.00E+13 n = .00 E = 37.58 }
2644
2645 NP16f: A2--C10H7 + O -> A2O-C10H7O { A = 1.00E+14 n = .00 E = .00 }
2646 NP17f: A2*-C10H7 + O -> A2O-C10H7O { A = 1.00E+14 n = .00 E = .00 }
2647
2648 NP18f: A2--C10H7 + OH -> A2O-C10H7O + H { A = 3.00E+13 n = .00 E = .00 }
2649 NP19f: A2*-C10H7 + OH -> A2O-C10H7O + H { A = 3.00E+13 n = .00 E = .00 }
2650
2651
2652 # Naphthol
2653 # Full rate for A1OH
2654 # ------------------
2655
2656 NP20f: A2OH-C10H8O -> C9H8 + CO { A = 8.62E+15 n = -0.61 E = 310.11 }
2657 NP21f: A2OH-C10H8O -> A2O-C10H7O + H { A = 1.01E+71 n =-15.92 E = 522.12 }
2658
2659 NP22f: A2OH-C10H8O + H -> A2O-C10H7O + H2 { A = 6.83E+01 n = 3.40 E = 30.26 }
2660 NP23f: A2OH-C10H8O + OH -> A2O-C10H7O + H2O { A = 1.73E+01 n = 3.40 E = -4.78 }
2661 NP24f: A2OH-C10H8O + CH3 -> A2O-C10H7O + CH4 { A = 3.70E-04 n = 4.70 E = 20.20 }
2662
2663
2664 # Naphthoxy radical
2665 # Full rate for A1O
2666 # -----------------
2667
2668 NP25f: A2O-C10H7O -> C9H7 + CO { A = 2.90E+10 n = .00 E = 152.40 }
2669 NP26 : A2O-C10H7O + O -> C9H6O + CO + H { A = 1.68E+14 n = .00 E = .00 }
2670 NP27 : A2O-C10H7O + O2 -> C9H6O + CO + OH { A = 6.51E+07 n = 1.30 E = 73.92 }
2671
2672
2673
2674 #=========================================================================#
2675 # #
2676 # alpha-MethylNaphthalene chemistry #
2677 # Adapted from Toluene chemistry #
2678 # #
2679 #=========================================================================#
2680
2681
2682 # MethylNaphthalene
2683 # -----------------
2684
2685 MN01f: A2CH3-C11H10 + H -> A2-C10H8 + CH3 { A = 2.31E+06 n = 2.17 E = 17.42 }
2686 MN02f: A2CH3-C11H10 + OH -> A2OH-C10H8O + CH3 { A = 7.83E+02 n = 2.88 E = 13.48 }
2687
2688 # Collision Limit at 298K
2689 MN03f: A2CH3-C11H10 -> A2CH2-C11H9 + H { A = 1.25E+18 n = -0.60 E = 396.59 }
2690 MN04f: A2CH3-C11H10 -> A2--C10H7 + CH3 { A = 3.20E+34 n = -5.02 E = 478.03 }
2691
2692 MN05f: A2CH2-C11H9 + H -> A2--C10H7 + CH3 { A = 5.83E+67 n =-14.15 E = 285.89 }
2693 MN06f: A2CH2-C11H9 -> C9H7 + C2H2 { A = 8.20E+14 n = .00 E = 337.55 }
2694
2695 MN07f: A2CH3-C11H10 + H -> A2CH2-C11H9 + H2 { A = 6.47E+00 n = 3.98 E = 14.16 }
2696 MN08f: A2CH3-C11H10 + O -> A2CH2-C11H9 + OH { A = 1.18E+00 n = 4.09 E = 10.65 }
2697 MN09f: A2CH3-C11H10 + OH -> A2CH2-C11H9 + H2O { A = 1.77E+05 n = 2.39 E = -2.52 }
2698 MN10f: A2CH3-C11H10 + O2 -> A2CH2-C11H9 + HO2 { A = 2.18E+07 n = 2.50 E = 192.65 }
2699 MN11f: A2CH3-C11H10 + CH3 -> A2CH2-C11H9 + CH4 { A = 1.73E+01 n = 3.44 E = 43.47 }
2700 MN12f: A2CH3-C11H10 + HO2 -> A2CH2-C11H9 + H2O2 { A = 9.33E+04 n = 2.50 E = 61.44 }
2701
2702 MN13 : A2CH3-C11H10 + O -> A2-C10H8 + CO + 2 H { A = 1.10E+13 n = .00 E = 18.96 }
2703 MN14 : A2CH3-C11H10 + O -> C9H7 + CH3 + CO { A = 1.47E+13 n = .00 E = 18.96 }
2704
2705
2706 # Methylene-Naphthyl
2707 # ------------------
2708
2709 MN15f: A2CH2-C11H9 + O -> A2-C10H8 + HCO { A = 6.98E+12 n = 0.33 E = 2.87 }
2710 MN16f: A2CH2-C11H9 + O -> A2CHO-C11H8O + H { A = 2.75E+13 n = 0.07 E = 3.06 }
2711 MN17f: A2CH2-C11H9 + O2 -> A2CHO-C11H8O + OH { A = 3.76E+15 n = -1.55 E = 47.37 }
2712 MN18f: A2CH2-C11H9 + HO2 -> A2CH2O-C11H9O + OH { A = 1.19E+09 n = 1.03 E = -9.41 }
2713
2714 MN19 : A2CH2-C11H9 + C3H3 -> A3-C14H10 + 2H { A = 1.88E+38 n = -7.53 E = 99.91 }
2715
2716
2717 # Methoxy-Naphthyl
2718 # ----------------
2719
2720 MN20f: A2CH2O-C11H9O -> A2CHO-C11H8O + H { A = 1.27E+13 n = .00 E = 86.19 }
2721 MN21f: A2CH2O-C11H9O -> A2--C10H7 + CH2O { A = 7.21E+33 n = -6.21 E = 154.18 }
2722
2723 MN22f: A2CH2O-C11H9O + H -> A2CHO-C11H8O + H2 { A = 1.33E+13 n = .00 E = .00 }
2724 MN23f: A2CH2O-C11H9O + O -> A2CHO-C11H8O + OH { A = 6.67E+12 n = .00 E = .00 }
2725 MN24f: A2CH2O-C11H9O + OH -> A2CHO-C11H8O + H2O { A = 3.33E+12 n = .00 E = .00 }
2726 MN25f: A2CH2O-C11H9O + O2 -> A2CHO-C11H8O + HO2 { A = 4.11E+10 n = .00 E = 7.32 }
2727
2728
2729 # Naphthaldehyde
2730 # --------------
2731
2732 MN26 : A2CHO-C11H8O -> A2--C10H7 + CO + H { A = 2.10E+16 n = .00 E = 342.00 }
2733
2734 MN27 : A2CHO-C11H8O + H -> A2--C10H7 + CO +H2 { A = 2.05E+09 n = 1.16 E = 10.06 }
2735 MN28 : A2CHO-C11H8O + O -> A2--C10H7 + CO +OH { A = 2.92E+12 n = .00 E = 7.57 }
2736 MN29 : A2CHO-C11H8O + OH -> A2--C10H7 + CO +H2O { A = 2.34E+10 n = 0.73 E = -4.66 }
2737 MN30 : A2CHO-C11H8O + CH3-> A2--C10H7 + CO +CH4 { A = 2.72E+06 n = 1.77 E = 24.77 }
2738
2739
2740
2741 #==========================================================================#
2742 # #
2743 # PAH chemistry #
2744 # HACA Based Mechanism #
2745 # #
2746 #==========================================================================#
2747
2748 # Fulvene
2749 # -------
2750
2751 # Jasper & Hansen 2013 - 1atm
2752 P01f: C5H4CH2 + H -> A1-C6H6 + H { A = 1.14E+32 n = -4.88 E = 79.05 }
2753
2754 # Senosiain & Miller 2007 (JPCA)
2755 P02f: N-C4H5 + C2H2 -> C5H4CH2 + H { A = 4.62E+15 n = -0.89 E = 38.25 }
2756 P03f: I-C4H5 + C2H2 -> C5H4CH2 + H { A = 6.80E+24 n = -3.45 E = 85.09 }
2757
2758 # Miller & Klippenstein 2003
2759 P04f: C5H4CH2 -> A1-C6H6 { A = 1.45E+45 n = -8.90 E = 405.86 }
2760 P05f: C5H4CH2 -> A1--C6H5 + H { A = 2.24E+68 n =-14.65 E = 596.54 }
2761
2762
2763 # Benzene
2764 # -------
2765
2766 # Wang & Frenklach 1997
2767 P06f: N-C4H3 + C2H2 -> A1--C6H5 { A = 9.60E+70 n =-17.77 E = 130.96 }
2768
2769 # Senosiain & Miller 2007 (JPCA)
2770 P07f: N-C4H5 + C2H2 -> A1-C6H6 + H { A = 1.38E+16 n = -1.00 E = 37.24 }
2771 P08f: I-C4H5 + C2H2 -> A1-C6H6 + H { A = 1.67E+23 n = -3.30 E = 104.43 }
2772
2773 # Miller, Klippenstein, Georgievskii, Harding, Allen, Simmonett 2010
2774 P09 : A-C3H5 + C3H3 -> C5H4CH2 + 2H { A = 1.88E+38 n = -7.53 E = 99.91 }
2775
2776 # Georgievskii, Miller, & Klippenstein 2007
2777 # -> Total rate at 1bar
2778 # Miller & Klippenstein 2003
2779 # -> Branching ratios
2780 # -> 2-ethynyl-1,3-butadiene lumped into Fulvene
2781 # Fitted rates valid for 800K-2000K - P=1bar
2782 P10f: C3H3 + C3H3 -> C5H4CH2 { A = 8.25E+46 n =-10.10 E = 70.96 }
2783 P11f: C3H3 + C3H3 -> A1-C6H6 { A = 1.07E+45 n = -9.57 E = 71.19 }
2784 P12f: C3H3 + C3H3 -> A1--C6H5 + H { A = 5.77E+37 n = -7.00 E = 131.82 }
2785
2786 # Tokmakov & Lin 2004
2787 P13f: A1--C6H5 + C2H4 -> A1-C6H6 + C2H3 { A = 9.45E-03 n = 4.47 E = 18.71 }
2788
2789
2790 # Naphthalene
2791 # -----------
2792
2793 # From A1 (x1/3)
2794 P14f: A1C2H-C8H6 + C2H -> A2--C10H7 { A = 6.67E+13 n = .00 E = .00 }
2795 P15f: A1C2H3-C8H8 + C2H -> A2-C10H8 + H { A = 6.67E+13 n = .00 E = .00 }
2796
2797 # Kislov & Mebel 2005
2798 P16f: A1C2H*-C8H5 + C2H2 -> A2--C10H7 { A = 1.34E+04 n = 2.50 E = 5.37 }
2799 P17f: A1C2H2-C8H7 + C2H2 -> A2-C10H8 + H { A = 2.62E+06 n = 2.00 E = 19.16 }
2800 P18f: A1C2H3*-C8H7 + C2H2 -> A2-C10H8 + H { A = 3.02E+03 n = 2.55 E = 13.31 }
2801
2802 # From A1 (x1/3)
2803 P19f: A1C2H-C8H6 + C2H3 -> A2-C10H8 + H { A = 4.50E+16 n = -1.15 E = 61.01 }
2804
2805 # From A1-
2806 P20f: A1C2H*-C8H5 + C2H4 -> A2-C10H8 + H { A = 3.62E+28 n = -4.24 E = 99.85 }
2807
2808 # Aguilera-Iparraguirre & Klopper 2007
2809 # Total entrance channel rate
2810 P21f: A1--C6H5 + C4H4 -> A2-C10H8 + H { A = 1.26E+04 n = 2.61 E = 6.00 }
2811
2812
2813 # From A1 (x2/3)
2814 P22f: A2-C10H8 + C2H -> A2C2HA-C12H8 + H { A = 1.67E+14 n = .00 E = .00 }
2815 P23f: A2-C10H8 + C2H -> A2C2HB-C12H8 + H { A = 1.67E+14 n = .00 E = .00 }
2816
2817 # Park, Nguyen, Xu, Lin 2009
2818 P24f: A2--C10H7 + C2H2 -> A2R5-C12H8 + H { A = 2.81E+07 n = 1.77 E = 9.37 }
2819 P25f: A2*-C10H7 + C2H2 -> A2C2HB-C12H8 + H { A = 5.38E+07 n = 1.65 E = 10.71 }
2820
2821 # From A1 (x2/3)
2822 P26f: A2-C10H8 + C2H3 -> A2C2H2A-C12H9 + H2 { A = 9.01E+16 n = -1.15 E = 61.01 }
2823 P27f: A2-C10H8 + C2H3 -> A2C2H2B-C12H9 + H2 { A = 9.01E+16 n = -1.15 E = 61.01 }
2824
2825 # From A1-
2826 P28f: A2--C10H7 + C2H4 -> A2C2H2A-C12H9 + H2 { A = 3.62E+28 n = -4.24 E = 99.85 }
2827 P29f: A2*-C10H7 + C2H4 -> A2C2H2B-C12H9 + H2 { A = 3.62E+28 n = -4.24 E = 99.85 }
2828
2829
2830 # From A1C2H2
2831 P30f: A2C2H2A-C12H9 -> A2C2HA-C12H8 + H { A = 1.81E+54 n =-12.69 E = 215.02 }
2832 P31f: A2C2H2A-C12H9 + H -> A2C2HA-C12H8 + H2 { A = 1.50E+13 n = .00 E = .00 }
2833 P32f: A2C2H2A-C12H9 + OH -> A2C2HA-C12H8 + H2O { A = 2.50E+12 n = .00 E = .00 }
2834
2835 P33f: A2C2H2B-C12H9 -> A2C2HB-C12H8 + H { A = 1.81E+54 n =-12.69 E = 215.02 }
2836 P34f: A2C2H2B-C12H9 + H -> A2C2HB-C12H8 + H2 { A = 1.50E+13 n = .00 E = .00 }
2837 P35f: A2C2H2B-C12H9 + OH -> A2C2HB-C12H8 + H2O { A = 2.50E+12 n = .00 E = .00 }
2838
2839 # From A1 (x1/6)
2840 P36f: A2C2HA-C12H8 -> A2C2HA*-C12H7 + H { A = 2.15E+60 n =-12.48 E = 619.55 }
2841 P37f: A2C2HA-C12H8 + H -> A2C2HA*-C12H7 + H2 { A = 1.00E+08 n = 1.80 E = 68.42 }
2842 P38f: A2C2HA-C12H8 + OH -> A2C2HA*-C12H7 + H2O { A = 3.90E+03 n = 2.68 E = 3.07 }
2843
2844 P39f: A2C2HB-C12H8 -> A2C2HB*-C12H7 + H { A = 2.15E+60 n =-12.48 E = 619.55 }
2845 P40f: A2C2HB-C12H8 + H -> A2C2HB*-C12H7 + H2 { A = 1.00E+08 n = 1.80 E = 68.42 }
2846 P41f: A2C2HB-C12H8 + OH -> A2C2HB*-C12H7 + H2O { A = 3.90E+03 n = 2.68 E = 3.07 }
2847
2848
2849 # Acenaphthalene
2850 # --------------
2851
2852 # Kislov & Mebel 2005
2853 P42f: A2C2H2A-C12H9 -> A2R5-C12H8 + H { A = 2.88E+11 n = 0.23 E = 71.24 }
2854
2855 # Lifshitz, Tambura & Dubnikova 2007
2856 P43f: A2C2HA-C12H8 + H -> A2R5-C12H8 + H { A = 3.52E+12 n = .00 E = 55.90 }
2857
2858 # From A1 (x2/3)
2859 P44f: A2R5-C12H8 -> A2R5--C12H7 + H { A = 8.60E+60 n =-12.48 E = 619.55 }
2860 P45f: A2R5-C12H8 + H -> A2R5--C12H7 + H2 { A = 4.01E+08 n = 1.80 E = 68.42 }
2861 P46f: A2R5-C12H8 + OH -> A2R5--C12H7 + H2O { A = 1.34E+04 n = 2.68 E = 3.07 }
2862
2863
2864 # From A1 (x2/3)
2865 P47f: A2R5-C12H8 + C2H -> A2R5C2H-C14H8 + H { A = 1.67E+14 n = .00 E = .00 }
2866
2867 # From A2*
2868 P48f: A2R5--C12H7 + C2H2 -> A2R5C2H-C14H8 + H { A = 5.38E+07 n = 1.65 E = 10.71 }
2869
2870 # From A1 (x2/3)
2871 P49f: A2R5-C12H8 + C2H3 -> A2R5C2H2-C14H9 + H2 { A = 9.01E+16 n = -1.15 E = 61.01 }
2872
2873 # From A1-
2874 P50f: A2R5--C12H7 + C2H4 -> A2R5C2H2-C14H9 + H2 { A = 3.62E+28 n = -4.24 E = 99.85 }
2875
2876
2877 # From A1C2H2
2878 P51f: A2R5C2H2-C14H9 -> A2R5C2H-C14H8 + H { A = 2.09E+38 n = -7.74 E = 196.19 }
2879 P52f: A2R5C2H2-C14H9 + H -> A2R5C2H-C14H8 + H2 { A = 1.65E+11 n = 0.49 E = 44.48 }
2880 P53f: A2R5C2H2-C14H9 + OH-> A2R5C2H-C14H8 + H2O { A = 2.50E+12 n = .00 E = .00 }
2881
2882 # From A1 (x1/6)
2883 P54f: A2R5C2H-C14H8 -> A2R5C2H*-C14H7 + H { A = 2.15E+60 n =-12.48 E = 619.55 }
2884 P55f: A2R5C2H-C14H8 + H -> A2R5C2H*-C14H7 + H2 { A = 1.00E+08 n = 1.80 E = 68.42 }
2885 P56f: A2R5C2H-C14H8 + OH-> A2R5C2H*-C14H7 + H2O { A = 3.90E+03 n = 2.68 E = 3.07 }
2886
2887
2888 # Biphenyl
2889 # --------
2890
2891
2892 # Park, Burova,, Rodgers & Lin 1999
2893 # Fitted exp rate
2894 P57f: A1-C6H6 + A1--C6H5 -> P2-C12H10 + H { A = 9.55E+11 n = .00 E = 9.07 }
2895
2896 # Tranter, Klippenstein, Harding, Giri, Yang, Keifer 2010
2897 P58f: A1--C6H5 + A1--C6H5 -> P2-C12H10 { A = 7.34E+20 n = -2.34 E = 17.26 }
2898 P59f: A1--C6H5 + A1--C6H5 -> P2--C12H9 + H { A = 2.44E+13 n = 0.89 E = 180.66 }
2899
2900 # From A1 (x2/3)
2901 P60f: P2-C12H10 -> P2--C12H9 + H { A = 8.60E+60 n =-12.48 E = 619.55 }
2902 P61f: P2-C12H10 + H -> P2--C12H9 + H2 { A = 4.01E+08 n = 1.80 E = 68.42 }
2903 P62f: P2-C12H10 + OH -> P2--C12H9 + H2O { A = 1.34E+04 n = 2.68 E = 3.07 }
2904
2905
2906 # Phenanthrene
2907 # ------------
2908
2909
2910 # From A1C2H3*
2911 P63f: P2--C12H9 + C2H2 -> A3-C14H10 + H { A = 3.02E+03 n = 2.55 E = 13.31 }
2912
2913 # From P2 (x1/3)
2914 P64f: A1C2H-C8H6 + A1--C6H5 -> A3-C14H10 + H { A = 3.18E+11 n = .00 E = 9.07 }
2915 # From P2 & P2-
2916 P65f: A1C2H*-C8H5 + A1-C6H6 -> A3-C14H10 + H { A = 9.55E+11 n = .00 E = 9.07 }
2917 P66f: A1C2H*-C8H5 + A1--C6H5 -> A3-C14H10 { A = 1.39E+13 n = .00 E = 0.47 }
2918
2919
2920 # From A1 (x1/6)
2921 P67f: A2C2HA-C12H8 + C2H -> A3--C14H9 { A = 3.33E+13 n = .00 E = .00 }
2922 P68f: A2C2HB-C12H8 + C2H -> A3--C14H9 { A = 3.33E+13 n = .00 E = .00 }
2923
2924 # From A1C2H*
2925 P69f: A2C2HA*-C12H7 + C2H2 -> A3*-C14H9 { A = 1.34E+04 n = 2.50 E = 5.37 }
2926 P70f: A2C2HB*-C12H7 + C2H2 -> A3*-C14H9 { A = 1.34E+04 n = 2.50 E = 5.37 }
2927
2928 # From A1C2H2
2929 P71f: A2C2H2A-C12H9 + C2H2 -> A3-C14H10 + H { A = 2.62E+06 n = 2.00 E = 19.16 }
2930 P72f: A2C2H2B-C12H9 + C2H2 -> A3-C14H10 + H { A = 2.62E+06 n = 2.00 E = 19.16 }
2931
2932 # From A1 (x1/6)
2933 P73f: A2C2HA-C12H8 + C2H3 -> A3-C14H10 + H { A = 2.25E+16 n = -1.15 E = 61.01 }
2934 P74f: A2C2HB-C12H8 + C2H3 -> A3-C14H10 + H { A = 2.25E+16 n = -1.15 E = 61.01 }
2935
2936 # From A1-
2937 P75f: A2C2HA*-C12H7 + C2H4 -> A3-C14H10 + H { A = 3.62E+28 n = -4.24 E = 99.85 }
2938 P76f: A2C2HB*-C12H7 + C2H4 -> A3-C14H10 + H { A = 3.62E+28 n = -4.24 E = 99.85 }
2939
2940 # From A1-
2941 P77f: A2--C10H7 + C4H4 -> A3-C14H10 + H { A = 1.26E+04 n = 2.61 E = 6.00 }
2942 P78f: A2*-C10H7 + C4H4 -> A3-C14H10 + H { A = 1.26E+04 n = 2.61 E = 6.00 }
2943
2944
2945 # From A1 (x1/3)
2946 P79f: A3-C14H10 -> A3*-C14H9 + H { A = 4.30E+60 n =-12.48 E = 619.55 }
2947 P80f: A3-C14H10 + H -> A3*-C14H9 + H2 { A = 2.00E+08 n = 1.80 E = 68.42 }
2948 P81f: A3-C14H10 + OH -> A3*-C14H9 + H2O { A = 7.80E+03 n = 2.68 E = 3.07 }
2949
2950 # From A1 (x2/3)
2951 P82f: A3-C14H10 -> A3--C14H9 + H { A = 8.60E+60 n =-12.48 E = 619.55 }
2952 P83f: A3-C14H10 + H -> A3--C14H9 + H2 { A = 4.01E+08 n = 1.80 E = 68.42 }
2953 P84f: A3-C14H10 + OH -> A3--C14H9 + H2O { A = 1.56E+04 n = 2.68 E = 3.07 }
2954
2955 # Frenklach 2005
2956 P85f: A3*-C14H9 -> A2R5--C12H7 + C2H2 { A = 1.30E+11 n = 1.08 E = 294.55 }
2957
2958
2959 # Acephenanthrylene
2960 # -----------------
2961
2962
2963 # From A1C2H*
2964 P86f: A2R5C2H*-C14H7 + C2H2 -> A3R5--C16H9 { A = 1.34E+04 n = 2.50 E = 5.37 }
2965
2966 # From A1C2H2
2967 P87f: A2R5C2H2-C14H9 + C2H2 -> A3R5-C16H10 + H { A = 2.62E+06 n = 2.00 E = 19.16 }
2968
2969 # From A2-
2970 P88f: A3--C14H9 + C2H2 -> A3R5-C16H10 + H { A = 2.81E+07 n = 1.77 E = 9.37 }
2971
2972 # From A1-
2973 P89f: A2R5--C12H7 + C4H4 -> A3R5-C16H10 + H { A = 1.26E+04 n = 2.61 E = 6.00 }
2974
2975
2976 # From A1 (x1/3)
2977 P90f: A3R5-C16H10 -> A3R5--C16H9 + H { A = 2.15E+60 n =-12.48 E = 619.55 }
2978 P91f: A3R5-C16H10 + H -> A3R5--C16H9 + H2 { A = 2.01E+08 n = 1.80 E = 68.42 }
2979 P92f: A3R5-C16H10 + OH -> A3R5--C16H9 + H2O { A = 7.80E+03 n = 2.68 E = 3.07 }
2980
2981
2982 # Pyrene
2983 # ------
2984
2985
2986 # From A2*
2987 P93f: A3*-C14H9 + C2H2 -> A4-C16H10 + H { A = 5.38E+07 n = 1.65 E = 10.71 }
2988
2989 # From A1 (x4/3)
2990 P94f: A4-C16H10 -> A4--C16H9 + H { A = 1.72E+60 n =-12.48 E = 619.55 }
2991 P95f: A4-C16H10 + H -> A4--C16H9 + H2 { A = 8.03E+08 n = 1.80 E = 68.42 }
2992 P96f: A4-C16H10 + OH -> A4--C16H9 + H2O { A = 3.12E+04 n = 2.68 E = 3.07 }
2993
2994
2995 # Cyclopenta[cd]pyrene
2996 # --------------------
2997
2998
2999 # From A2-/A2*
3000 P97f: A4--C16H9 + C2H2 -> A4R5-C18H10 + H { A = 2.81E+07 n = 1.77 E = 9.37 }
3001 P98f: A3R5--C16H9 + C2H2 -> A4R5-C18H10 + H { A = 5.38E+07 n = 1.65 E = 10.71 }
3002
3003
3004 # Fluoranthene
3005 # ------------
3006
3007
3008 # From A1+A1- (x2/3 and x1)
3009 P99 : A2-C10H8 + A1--C6H5 -> FLTN-C16H10 + H2+H { A = 6.37E+11 n = .00 E = 9.07 }
3010 P100: A2--C10H7 + A1-C6H6 -> FLTN-C16H10 + H2+H { A = 9.55E+11 n = .00 E = 9.07 }
3011
3012 # From A1-+A1-
3013 P101: A2--C10H7 + A1--C6H5 -> FLTN-C16H10 + 2H { A = 1.39E+13 n = .00 E = 0.47 }
3014
3015
3016
3017 #==========================================================================#
3018 # #
3019 # Higher PAH Oxidation Chemistry #
3020 # Adapted from Benzene #
3021 # #
3022 #==========================================================================#
3023
3024 # From A1-+O2
3025 OX01 : A3*-C14H9 + O2 -> A2C2H2B-C12H9 + 2CO { A = 8.57E+20 n = -2.27 E = 30.08 }
3026 OX02 : A3--C14H9 + O2 -> A2C2H2A-C12H9 + 2CO { A = 8.57E+20 n = -2.27 E = 30.08 }
3027 OX03 : A4--C16H9 + O2 -> A3*-C14H9 + 2CO { A = 8.57E+20 n = -2.27 E = 30.08 }
3028 OX04 : A2R5--C12H7 + O2 -> A2--C10H7 + 2CO { A = 8.57E+20 n = -2.27 E = 30.08 }
3029 OX05 : A3R5--C16H9 + O2 -> A3*-C14H9 + 2CO { A = 8.57E+20 n = -2.27 E = 30.08 }
3030
3031 # From A1+OH
3032 # Rescaled by number of active sites
3033 OX06 : A3-C14H10 + OH -> A2C2HA-C12H8 +CH3+CO { A = 1.10E+02 n = 3.25 E = 23.39 }
3034 OX07 : A3-C14H10 + OH -> A2C2HB-C12H8 +CH3+CO { A = 1.10E+02 n = 3.25 E = 23.39 }
3035 OX08 : A4-C16H10 + OH -> A3-C14H10 + HCCO { A = 2.20E+02 n = 3.25 E = 23.39 }
3036 OX09 : A2R5-C12H8 + OH -> A2-C10H8 + HCCO { A = 1.76E+02 n = 3.25 E = 23.39 }
3037 OX10 : A3R5-C16H10 + OH -> A3-C14H10 + HCCO { A = 2.20E+02 n = 3.25 E = 23.39 }
3038 OX11 : A4R5-C18H10 + OH -> A4-C16H10 + HCCO { A = 2.20E+02 n = 3.25 E = 23.39 }
3039 OX12 : FLTN-C16H10 + OH -> A3-C14H10 + HCCO { A = 2.20E+02 n = 3.25 E = 23.39 }
3040
3041
3042
3043 #================================================================#
3044 # #
3045 # Soot Formation #
3046 # #
3047 #================================================================#
3048
3049 ###### H-Abstraction ######
3050
3051 # Tokmakov & Lin 1999/2002
3052 # Rates indep of pressure
3053 # 1/6 of forward and full backward
3054 SOOT1f: Soot-CH + OH -> Soot-C + H2O { A = 6.72E+01 n = 3.33 E = 6.09 }
3055 SOOT1b: Soot-C + H2O -> Soot-CH + OH { A = 6.44E-01 n = 3.79 E = 27.96 }
3056
3057 # Mebel & Lin 1997
3058 # Rates indep of pressure
3059 # 1/6 of forward and full backward
3060 SOOT2f: Soot-CH + H -> Soot-C + H2 { A = 1.00E+08 n = 1.80 E = 68.42 }
3061 SOOT2b: Soot-C + H2 -> Soot-CH + H { A = 8.68E+04 n = 2.36 E = 25.46 }
3062
3063 # Harding, Georgievskii & Klippenstein 2005
3064 # High Pressure Limit
3065 # 1/6 of forward and full backward
3066 SOOT3f: Soot-CH -> Soot-C + H { A = 1.13E+16 n = -0.06 E = 476.05 }
3067 SOOT3b: Soot-C + H -> Soot-CH { A = 4.17E+13 n = 0.15 E = .00 }
3068
3069
3070 ###### C2H2-Addition ######
3071
3072 # Tokmakov & Lin 2004
3073 # High pressure rates for A1- + C2H2 <=> A1C2H2 (x2)
3074 SOOT4: Soot-C + C2H2 -> Soot-CH noCheck { A = 2.52E+09 n = 1.10 E = 17.13 }
3075
3076
3077 ###### Oxidation ######
3078
3079 # Assume first reaction step is the limiting step:
3080 # Attack by O2 or OH
3081
3082 # Kazakov, Wang & Frenklach 1995
3083 SOOT5: Soot-C + O2 -> Soot-C + 2CO noCheck { A = 2.20E+12 n = .00 E = 31.38 }
3084
3085 # Sarofim 1981
3086 # Directly Coded in FlameMaster
3087 # From collision efficiency - 0.13
3088 SOOT6 : Soot-CH + OH -> Soot-C + CO noCheck { A = 0.00E+00 n = .00 E = .00 }
3089
3090
3091 # **** Third Body *****
3092
3093 Let M0 = 1.0 [OTHER].
3094
3095 Let M1 = 0.0 [H2] + 0.0 [H2O] + 0.63 [AR] + 0.00 [CO2] + 1.0 [OTHER].
3096 Let M2 = 2.5 [H2] + 12.0 [H2O] + 0.75 [AR] + 1.0 [OTHER].
3097 Let M3 = 2.5 [H2] + 12.0 [H2O] + 0.00 [AR] + 1.0 [OTHER].
3098 Let M4 = 1.5 [H2] + 11.7 [H2O] + 0.52 [AR] + 1.09 [CO] + 2.18 [CO2] + 0.89 [O2] + 1.0 [OTHER].
3099 Let M5 = 3.0 [H2] + 0.0 [H2O] + 2.00 [N2] + 1.50 [O2] + 1.0 [OTHER].
3100 Let M6 = 2.5 [H2] + 9.0 [H2O] + 1.50 [N2] + 1.0 [OTHER].
3101
3102 Let M7 = 2.0 [H2] + 12.0 [H2O] + 0.70 [AR] + 1.75 [CO] + 3.60 [CO2] + 1.0 [OTHER].
3103 Let M8 = 2.0 [H2] + 0.0 [H2O] + 1.75 [CO] + 3.60 [CO2] + 1.0 [OTHER].
3104
3105 Let M9 = 2.0 [H2] + 6.0 [H2O] + 0.70 [AR] + 1.50 [CO] + 2.00 [CO2] + 2 [CH4] + 3 [C2H6] + 1.0 [OTHER].
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