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Revision 2.3 - (show annotations) (download)
Wed Mar 25 01:15:43 2015 UTC (9 years ago) by gblanqu
Branch: MAIN
CVS Tags: HEAD
Changes since 2.2: +305 -312 lines
Reactions
-C2H5+OH: reaction removed
-A1CHO+H: CH2O displacement reaction added

Rates/products
-CH3+O: products and rates updated
-CH3+OH: rates updated
-C2H4+CH3: rate corrected
-C4H4+CH3: rate revised based on C2H4
-C4H6+CH3: rate revised based on C2H4
-DC4H6+X: rates/reactions revised based on C3H6
-OC6H11OOH decomp: products fixed
-A1OH+X: rates revised from revised CH3OH
-A1CH2O decomp: HPL rate replaced by 1atm rate
-HOA1CH3+X: rates revised from revised CH3OH
-A2CH2O decomp: rate revised from revised A1CH2O

Revised CH3OH submodel
-whole CH3OH PES revised (products and rates)
-CH3O+O2: updated rate
-CH2OH+O2: updated rate
-CH3OH+H/OH/CH3/O2/HO2: updated rates

Revised/simplified C3H4/C3H5 submodel
-reactions re-ordered
-AC3H4+CH3: rate updated because of C2H4+CH3
-C3H4+C2H: reactions removed
-C6H10/C6H9 species/reactions removed
-AC3H5+O: rates and products updated
-AC3H5+OH/HCO/HO2: reactions removed
-TC3H5+R: reactions added/revised based on C2H3/C2H5
-SC3H5+R: reactions added/revised based on C2H3
-C3H6 decomp: rates and products updated
-C3H6+H/CH3: rates revised based on smaller HC
-C3H6+OH: rates revised from newer litt.
1 Let allowed atoms be C, H, O, N, AR.
2 Let additional species be N2.
3 Let temperature exponent be n_k.
4 Let order of reaction be n.
5 Let units for A be [ cm^(3(n-1)) / ( s * mole^(n-1) * K^n_k ) ].
6 Let units for E be [ kJ / mole ].
7 Let symbol for soot be SOOT.
8
9
10 #=========================================================================#
11 # #
12 # "An Improved H2/O2 Mechanism #
13 # based on Recent Shock Tube/Laser Absorption Measurements" #
14 # Hong, Davidson, Hanson, Combust. Flame (2011) #
15 # #
16 #=========================================================================#
17
18
19 # Hydrogen/oxygen
20 # ---------------
21
22 1f: H + O2 -> O + OH { A = 1.04E+14 n = .00 E = 63.96 }
23 2f: O + H2 -> H + OH { A = 3.82E+12 n = .00 E = 33.25 }
24 3f: O + H2 -> H + OH { A = 8.79E+14 n = .00 E = 80.21 }
25 4f: OH + H2 -> H + H2O { A = 2.17E+08 n = 1.52 E = 14.46 }
26 5f: OH + OH -> O + H2O { A = 3.57E+04 n = 2.40 E = -8.83 }
27
28 # Davis et al. 2005
29 6f: 2 H + M1 -> H2 + M1 { A = 1.78E+18 n = -1.00 E = .00 }
30 7f: 2 H + H2 -> H2 + H2 { A = 9.00E+16 n = -0.60 E = .00 }
31 8f: 2 H + H2O -> H2 + H2O { A = 5.62E+19 n = -1.25 E = .00 }
32 9f: 2 H + CO2 -> H2 + CO2 { A = 5.50E+20 n = -2.00 E = .00 }
33
34 10f: O + H + M2 -> OH + M2 { A = 4.71E+18 n = -1.00 E = .00 }
35 11f: O + O + M3 -> O2 + M3 { A = 6.16E+15 n = -0.50 E = .00 }
36 12f: O + O + AR -> O2 + AR { A = 1.89E+13 n = .00 E = -7.48 }
37
38 # All rates recombined into a single
39 # Similar to Davis et al. 2005
40 # Collider efficiency evaluated at 1200K
41 13f: H + O2 + M4 -> HO2 + M4 { Ai= 5.59E+13 ni= 0.20 Ei= .00
42 A = 2.65E+19 n = -1.30 E = .00
43 fca = 0.3 fcta = 1.0E-10
44 fcb = 0.7 fctb = 1.0E+10
45 fcc = 1.0 fctc = 1.0E+10 }
46
47 14f: H2O + M5 -> OH + H + M5 { A = 6.06E+27 n = -3.31 E = 505.30 }
48 15f: H2O + H2O -> OH + H + H2O { A = 1.00E+26 n = -2.44 E = 502.75 }
49
50
51 # Hydroperoxy radical
52 # -------------------
53
54 16f: HO2 + H -> H2 + O2 { A = 3.66E+06 n = 2.09 E = -6.07 }
55 17f: HO2 + H -> O + H2O { A = 1.45E+12 n = .00 E = .00 }
56 18f: HO2 + H -> OH + OH { A = 7.08E+13 n = .00 E = 1.26 }
57 19f: HO2 + O -> OH + O2 { A = 1.63E+13 n = .00 E = -1.86 }
58
59 20f: HO2 + OH -> H2O + O2 { A = 2.89E+13 n = .00 E = -2.09 }
60 21f: HO2 + HO2 -> H2O2 + O2 { A = 1.30E+11 n = .00 E = -6.71 }
61 22f: HO2 + HO2 -> H2O2 + O2 { A = 4.20E+14 n = .00 E = 50.12 }
62
63
64 # Hydrogen peroxide
65 # -----------------
66
67 # Low P from Hong et al. 2011 - refitted
68 # Rest from Davis et al. 2005
69 23f: 2 OH + M6 -> H2O2 + M6 { A = 2.73E+19 n = -1.50 E = -9.59
70 Ai= 1.11E+14 ni= -0.37 Ei= .00
71 fcA = 0.2654 fctA = 94
72 fcb = 0.7346 fctb = 1756
73 fcc = 1.0 fctc = 5182 }
74
75 24f: H2O2 + H -> H2O + OH { A = 1.02E+13 n = .00 E = 14.97 }
76 25f: H2O2 + H -> HO2 + H2 { A = 1.21E+07 n = 2.00 E = 21.76 }
77 26f: H2O2 + O -> HO2 + OH { A = 8.43E+11 n = .00 E = 16.61 }
78 27f: H2O2 + OH -> HO2 + H2O { A = 1.74E+12 n = .00 E = 1.33 }
79 28f: H2O2 + OH -> HO2 + H2O { A = 7.59E+13 n = .00 E = 29.77 }
80
81
82
83 #=========================================================================#
84 # #
85 # "An optimized kinetic model of H2/CO combustion" #
86 # Davis, Joshi, Wang, and Egolfopoulos #
87 # Proc. Comb. Inst. 30 (2005) 1283-1292 #
88 # #
89 #=========================================================================#
90
91
92 # Carbon oxides
93 # -------------
94
95 30f: CO + O + M7 -> CO2 + M7 { A = 1.17E+24 n = -2.79 E = 17.54
96 Ai= 1.36E+10 ni= .00 Ei= 9.97
97 fcc = 1.0 fctc = 0.0 }
98 31f: CO + OH -> CO2 + H { A = 8.00E+11 n = 0.14 E = 30.76 }
99 32f: CO + OH -> CO2 + H { A = 8.78E+10 n = 0.03 E = -0.07 }
100 33f: CO + O2 -> CO2 + O { A = 1.12E+12 n = .00 E = 199.58 }
101 34f: CO + HO2 -> CO2 + OH { A = 3.01E+13 n = .00 E = 96.23 }
102
103 35f: HCO + M8 -> CO + H + M8 { A = 1.87E+17 n = -1.00 E = 71.13 }
104 36f: HCO + H2O -> CO + H + H2O { A = 2.24E+18 n = -1.00 E = 71.13 }
105
106 37f: HCO + H -> CO + H2 { A = 1.20E+14 n = .00 E = .00 }
107 38f: HCO + O -> CO + OH { A = 3.00E+13 n = .00 E = .00 }
108 39f: HCO + OH -> CO + H2O { A = 3.02E+13 n = .00 E = .00 }
109
110 40f: HCO + O -> CO2 + H { A = 3.00E+13 n = .00 E = .00 }
111
112 # New fit to experimental data
113 # Colbergs & Friedrichs 2006
114 41f: HCO + O2 -> CO + HO2 { A = 5.31E+10 n = 0.69 E = -0.52 }
115
116
117
118 #=========================================================================#
119 # #
120 # Kinetics of Excited states compiled mostly from #
121 # Kathrotia, Fikri, Bozkurt, Hartmann, Riedel, Schulz - Comb. Flame 2010 #
122 # Bozkurt, Fiki, Schulz - Appl Phys B (2012) #
123 # (some rates reduced to collison limit) #
124 # #
125 #=========================================================================#
126
127
128 # Excited OH*
129 # -----------
130
131 # Reduced by 2 to match abs values
132 E01f: O + H + M10 -> S-OH + M10 { A = 3.00E+12 n = .00 E = 25.00 }
133 E02f: CH + O2 -> S-OH + CO { A = 8.00E+10 n = .00 E = .00 }
134
135 E03f: S-OH -> OH { A = 1.45E+06 n = .00 E = .00 }
136 E04f: S-OH + AR -> OH + AR { A = 1.69E+12 n = .00 E = 17.32 }
137 E05f: S-OH + N2 -> OH + N2 { A = 1.08E+11 n = 0.50 E = -5.19 }
138 E06f: S-OH + O2 -> OH + O2 { A = 2.10E+12 n = 0.50 E = -2.02 }
139 E07f: S-OH + H2O -> OH + H2O { A = 1.55E+12 n = 0.50 E = -3.61 }
140 E08f: S-OH + CO -> OH + CO { A = 2.28E+12 n = 0.50 E = -3.30 }
141 E09f: S-OH + CO2 -> OH + CO2 { A = 1.61E+12 n = 0.50 E = -4.06 }
142
143
144 # Excited CH*
145 # -----------
146
147 E11f: C + H + M0 -> S-CH + M0 { A = 3.63E+13 n = .00 E = .00 }
148
149 # Devreindt, Peeters et al. 1997
150 E12f: C2H + O -> S-CH + CO { A = 1.44E+13 n = .00 E = 1.91 }
151
152 E13f: S-CH -> CH { A = 1.86E+06 n = .00 E = .00 }
153 E14f: S-CH + AR -> CH + AR { A = 3.13E+11 n = .00 E = .00 }
154 E15f: S-CH + N2 -> CH + N2 { A = 3.03E+02 n = 3.40 E = -1.70 }
155 E16f: S-CH + O2 -> CH + O2 { A = 2.48E+06 n = 2.14 E = -7.20 }
156 E17f: S-CH + H2O -> CH + H2O { A = 5.30E+13 n = .00 E = .00 }
157 E18f: S-CH + CO -> CH + CO { A = 2.44E+12 n = 0.50 E = .00 }
158 E19f: S-CH + CO2 -> CH + CO2 { A = 2.40E-01 n = 4.30 E = -7.10 }
159
160
161
162 #=========================================================================#
163 # #
164 # GRI-MECH version 3.0 #
165 # http://www.me.berkeley.edu/gri_mech/ #
166 # #
167 # Gregory P. Smith, David M. Golden, Michael Frenklach, Nigel W. Moriarty #
168 # Boris Eiteneer, Mikhail Goldenberg, C. Thomas Bowman, Ronald K. Hanson, #
169 # Soonho Song, William C. Gardiner, Jr., Vitali V. Lissianski, Zhiwei Qin #
170 # #
171 #=========================================================================#
172
173 # Carbon
174 # ------
175
176 G01f: C + OH -> CO + H { A = 5.00E+13 n = .00 E = .00 }
177 G02f: C + O2 -> CO + O { A = 5.80E+13 n = .00 E = 2.41 }
178
179
180 # Methylidyne
181 # -----------
182
183 # Back to value before GRI opt
184 # Dean, Davidson, Hanson 1991
185 G03f: CH + H -> C + H2 { A = 1.10E+14 n = .00 E = .00 }
186
187 G04f: CH + O -> CO + H { A = 5.70E+13 n = .00 E = .00 }
188 G05f: CH + OH -> HCO + H { A = 3.00E+13 n = .00 E = .00 }
189 G06f: CH + H2 -> T-CH2 + H { A = 1.08E+14 n = .00 E = 13.01 }
190 G07f: CH + H2 + M9 -> CH3 + M9 { A = 4.82E+25 n = -2.80 E = 2.47
191 Ai= 1.97E+12 ni= 0.43 Ei= -1.55
192 fcA = 0.422 fctA = 122
193 fcb = 0.578 fctb = 2535
194 fcc = 1.0 fctc = 9365 }
195 G08f: CH + H2O -> CH2O + H { A = 5.71E+12 n = .00 E = -3.16 }
196 G09f: CH + O2 -> HCO + O { A = 6.71E+13 n = .00 E = .00 }
197 G10f: CH + CO + M9 -> HCCO + M9 { A = 2.69E+28 n = -3.74 E = 8.10
198 Ai= 5.00E+13 ni= .00 Ei= .00
199 fcA = 0.4243 fctA = 237
200 fcb = 0.5757 fctb = 1652
201 fcc = 1.0 fctc = 5069 }
202 G11f: CH + CO2 -> HCO + CO { A = 1.90E+14 n = .00 E = 66.07 }
203
204
205 # Methylene (triplet)
206 # -------------------
207
208 # Ai reduced due to collision limit
209 G12f: T-CH2 + H + M9 -> CH3 + M9 { A = 1.04E+26 n = -2.76 E = 6.69
210 Ai= 4.19E+14 ni= .00 Ei= .00
211 fcA = 0.438 fctA = 91
212 fcb = 0.562 fctb = 5836
213 fcc = 1.0 fctc = 8552 }
214 G13f: T-CH2 + O -> HCO + H { A = 8.00E+13 n = .00 E = .00 }
215 G14f: T-CH2 + OH -> CH2O + H { A = 2.00E+13 n = .00 E = .00 }
216 G15f: T-CH2 + OH -> CH + H2O { A = 1.13E+07 n = 2.00 E = 12.55 }
217 G16f: T-CH2 + H2 -> CH3 + H { A = 5.00E+05 n = 2.00 E = 30.25 }
218
219 # Alvarez, Moore, 1994
220 # Lee, Matsui, Chen, Wang 2012
221 # (revised branching ratios 0.58/0.20/0.22)
222 G17f: T-CH2 + O2 -> HCO + OH { A = 9.57E+12 n = .00 E = 7.27 }
223 G18f: T-CH2 + O2 -> CH2O + O { A = 3.30E+12 n = .00 E = 7.27 }
224 G19f: T-CH2 + O2 -> CO2 + H2 { A = 3.63E+12 n = .00 E = 7.27 }
225
226 G20f: T-CH2 + HO2 -> CH2O + OH { A = 2.00E+13 n = .00 E = .00 }
227 G21f: T-CH2 + C -> C2H + H { A = 5.00E+13 n = .00 E = .00 }
228 G22f: T-CH2 + CO + M9 -> CH2CO + M9 { A = 2.69E+33 n = -5.11 E = 29.69
229 Ai= 8.10E+11 ni= .50 Ei= 18.87
230 fcA = 0.4093 fctA = 275
231 fcb = 0.5907 fctb = 1226
232 fcc = 1.0 fctc = 5185 }
233 G23f: T-CH2 + CH -> C2H2 + H { A = 4.00E+13 n = .00 E = .00 }
234 G24f: T-CH2 + T-CH2 -> C2H2 + H2 { A = 1.60E+15 n = .00 E = 49.97 }
235 G25 : T-CH2 + T-CH2 -> C2H2 + 2 H { A = 2.00E+14 n = .00 E = 45.98 }
236
237
238 # Methylene (singlet)
239 # -------------------
240
241 G26f: S-CH2 + N2 -> T-CH2 + N2 { A = 1.50E+13 n = .00 E = 2.51 }
242 G27f: S-CH2 + AR -> T-CH2 + AR { A = 9.00E+12 n = .00 E = 2.51 }
243 G28f: S-CH2 + CO -> T-CH2 + CO { A = 9.00E+12 n = .00 E = .00 }
244 G29f: S-CH2 + CO2 -> T-CH2 + CO2 { A = 7.00E+12 n = .00 E = .00 }
245 G30f: S-CH2 + H2O -> T-CH2 + H2O { A = 3.00E+13 n = .00 E = .00 }
246
247 G31f: S-CH2 + H -> CH + H2 { A = 3.00E+13 n = .00 E = .00 }
248 G32f: S-CH2 + O -> CO + H2 { A = 1.50E+13 n = .00 E = .00 }
249 G33f: S-CH2 + O -> HCO + H { A = 1.50E+13 n = .00 E = .00 }
250 G34f: S-CH2 + H2 -> CH3 + H { A = 7.00E+13 n = .00 E = .00 }
251 G35 : S-CH2 + O2 -> CO + OH + H { A = 2.80E+13 n = .00 E = .00 }
252 G36f: S-CH2 + O2 -> CO + H2O { A = 1.20E+13 n = .00 E = .00 }
253
254 G37f: S-CH2 + OH -> CH2O + H { A = 3.00E+13 n = .00 E = .00 }
255 G38 : S-CH2 + H2O -> CH2O + H2 { A = 6.82E+10 n = .25 E = -3.91 }
256 G39f: S-CH2 + CO2 -> CH2O + CO { A = 1.40E+13 n = .00 E = .00 }
257
258
259 # Formaldehyde
260 # ------------
261
262 # Fridrichs, Davidson, Hanson 2004
263 # k0 fitted to reproduce k(1atm) - Same Fc as before
264 G40f: CH2O + M9 -> HCO + H + M9 { A = 1.11E+40 n = -6.42 E = 420.33
265 Ai= 8.36E+17 ni= -0.50 Ei= 373.00
266 fcA = 0.2176 fctA = 271
267 fcb = 0.7824 fctb = 2755
268 fcc = 1.0 fctc = 6570 }
269 G41f: CH2O + M9 -> CO + H2 + M9 { A = 1.47E+45 n = -7.83 E = 405.10
270 Ai= 1.23E+14 ni= .00 Ei= 347.00
271 fcA = 0.068 fctA = 197
272 fcb = 0.932 fctb = 1540
273 fcc = 1.0 fctc = 10300 }
274
275 # Wang, Dames, Davidson, Hanson 2014
276 G42f: CH2O + H -> HCO + H2 { A = 5.86E+03 n = 3.13 E = 6.34 }
277
278 # Xu, Zhu, Lin 2006
279 G43f: CH2O + OH -> HCO + H2O { A = 1.94E+06 n = 2.11 E = -7.06 }
280
281 G44f: CH2O + O -> HCO + OH { A = 3.90E+13 n = .00 E = 14.81 }
282 G45f: CH2O + O2 -> HCO + HO2 { A = 1.00E+14 n = .00 E = 167.36 }
283 G46f: CH2O + HO2 -> HCO + H2O2 { A = 5.60E+06 n = 2.00 E = 50.21 }
284
285 # Nguyen, Nguyen, Nguyen, Hoang, Vereecken 2014
286 # (reduced due to collision limit)
287 G47f: CH2O + CH -> CH2CO + H { A = 2.68E+14 n = -0.32 E = -3.21 }
288
289
290 # Methyl radical
291 # --------------
292
293 # Golden 2013
294 # Baulch et al.; Troe Ushakov
295 G48f: CH3 + H + M9 -> CH4 + M9 { A = 2.79E+34 n = -5.10 E = 11.65
296 Ai= 4.36E+13 ni= 0.19 Ei= .00
297 fcA = 0.37 fctA = 61
298 fcb = 0.63 fctb = 3315
299 fcc = 1.0 fctc = 1e10 }
300
301 # Harding, Klippenstein, Georgievskii 2005 - Total rate
302 # Xu, Ragunath, Lin 2015 - Branching ratios
303 G49f: CH3 + O -> CH2O + H { A = 3.32E+13 n = 0.05 E = -0.57 }
304 G50f: CH3 + O -> HCO + H2 { A = 2.22E+13 n = 0.05 E = -0.57 }
305
306 # Jasper, Klippenstein, Harding, Ruscic 2007 - fitted 1atm
307 # rate for S-CH2 80% larger than Xu, Xu, Lin 2007
308 G51f: CH3 + OH -> T-CH2 + H2O { A = 4.24E+04 n = 2.57 E = 16.73 }
309 G52f: CH3 + OH -> S-CH2 + H2O { A = 1.81E+15 n = -0.77 E = 5.54 }
310
311 # Petersen et al. 2007
312 G53f: CH3 + O2 -> CH3O + O { A = 1.38E+13 n = .00 E = 127.70 }
313 G54f: CH3 + O2 -> CH2O + OH { A = 5.87E+11 n = .00 E = 57.91 }
314 G55f: CH3 + O2 + M0 -> CH3O2 + M0 { A = 3.82E+31 n = -4.89 E = 14.36
315 Ai= 1.01E+08 ni= 1.63 Ei= .00
316 fca = 0.955 fcta = 880.1
317 fcb = 0.045 fctb = 2.5E+9
318 fcc = 1 fctc = 1.786E+09 }
319 G56f: CH3O2 + CH3 -> CH3O + CH3O { A = 1.00E+13 n = .00 E = -5.02 }
320 G57 : CH3O2 + CH3O2 -> CH3O + CH3O + O2 { A = 1.40E+16 n = -1.61 E = 7.78 }
321 G58 : CH3O2 + HO2 -> CH3O + OH + O2 { A = 2.47E+11 n = .00 E = -6.57 }
322 G59 : CH3O2 + CH2O -> CH3O + OH + HCO { A = 1.99E+12 n = .00 E = 48.83 }
323
324 # Jasper, Klippensteion, Harding 2009
325 G60f: CH3 + HO2 -> CH3O + OH { A = 1.00E+12 n = 0.29 E = -2.87 }
326 G61f: CH3 + HO2 -> CH4 + O2 { A = 1.19E+05 n = 2.23 E = -12.65 }
327
328 G62f: CH3 + H2O2 -> CH4 + HO2 { A = 2.45E+04 n = 2.47 E = 21.67 }
329 G63f: CH3 + HCO -> CH4 + CO { A = 2.65E+13 n = .00 E = .00 }
330 G64f: CH3 + CH2O -> CH4 + HCO { A = 3.32E+03 n = 2.81 E = 24.52 }
331
332 G65f: CH3 + C -> C2H2 + H { A = 5.00E+13 n = .00 E = .00 }
333 G66f: CH3 + CH -> C2H3 + H { A = 3.00E+13 n = .00 E = .00 }
334 G67f: CH3 + T-CH2 -> C2H4 + H { A = 1.00E+14 n = .00 E = .00 }
335 G68f: CH3 + S-CH2 -> C2H4 + H { A = 1.20E+13 n = .00 E = -2.39 }
336 G69f: CH3 + CH3 -> C2H5 + H { A = 6.84E+12 n = 0.10 E = 44.35 }
337
338
339 # Methoxy/hydroxymethyl radicals
340 # ------------------------------
341
342 # Dames & Golden 2013
343 G70f: CH2OH + M11 -> CH2O + H + M11 { A = 3.50E+21 n = -1.99 E = 100.41
344 Ai= 7.37E+10 ni= 0.81 Ei= 165.61
345 fcA = 0.156 fctA = 900
346 fcb = 0.844 fctb = 1
347 fcc = 1.0 fctc = 3315 }
348 G71f: CH3O + M11 -> CH2O + H + M11 { A = 6.02E+16 n = -0.55 E = 75.41
349 Ai= 1.13E+10 ni= 1.21 Ei= 100.77
350 fcA = 0.659 fctA = 28
351 fcb = 0.341 fctb = 1000
352 fcc = 1.0 fctc = 2339 }
353
354
355 # Xu, Xu, Lin 2007
356 G72f: CH3O + H -> CH3 + OH { A = 4.65E+13 n = 0.28 E = 0.12 }
357 G73f: CH2OH + H -> CH3 + OH { A = 1.82E+13 n = 0.16 E = 0.47 }
358 G74f: CH3O + H -> CH2O + H2 { A = 7.59E+08 n = 1.50 E = -2.17 }
359 G75f: CH2OH + H -> CH2O + H2 { A = 4.01E+06 n = 1.86 E = 0.62 }
360
361 G76f: CH3O + O -> CH2O + OH { A = 1.00E+13 n = .00 E = .00 }
362 G77f: CH3O + OH -> CH2O + H2O { A = 5.00E+12 n = .00 E = .00 }
363
364 # Chai, Hu, Dibble 2014
365 G78f: CH3O + O2 -> CH2O + HO2 { A = 2.29E+03 n = 2.40 E = 1.73 }
366
367 G79f: CH2OH + O -> CH2O + OH { A = 1.00E+13 n = .00 E = .00 }
368 G80f: CH2OH + OH -> CH2O + H2O { A = 5.00E+12 n = .00 E = .00 }
369
370 # Grotheer et al. 1988
371 G81f: CH2OH + O2 -> CH2O + HO2 { A = 2.41E+14 n = .00 E = 20.99 }
372
373
374 # Methane
375 # -------
376
377 G82f: CH4 + H -> CH3 + H2 { A = 6.60E+08 n = 1.62 E = 45.36 }
378 G83f: CH4 + O -> CH3 + OH { A = 1.02E+09 n = 1.50 E = 35.98 }
379 G84f: CH4 + OH -> CH3 + H2O { A = 1.00E+08 n = 1.60 E = 13.05 }
380 G85f: CH4 + T-CH2 -> CH3 + CH3 { A = 2.46E+06 n = 2.00 E = 34.60 }
381 G86f: CH4 + S-CH2 -> CH3 + CH3 { A = 1.60E+13 n = .00 E = -2.39 }
382
383 G87f: CH4 + CH -> C2H4 + H { A = 6.00E+13 n = .00 E = .00 }
384
385
386 # Methanol
387 # --------
388
389 # Jasper, Klippenstein, Harding, Ruscic 2007 - refitted
390 G90f: CH3OH + M9 -> CH3 + OH + M9 { A = 5.39E+51 n = -9.36 E = 435.03
391 Ai= 2.08E+18 ni= -0.61 Ei= 387.21
392 fcA = 0.2344 fctA = 59.51
393 fcb = 0.7656 fctb = 1910
394 fcc = 1.0 fctc = 9374 }
395 G91f: CH3OH + M9 -> S-CH2 + H2O + M9 { A = 7.76E+48 n = -8.68 E = 420.25
396 Ai= 3.12E+18 ni= -1.02 Ei= 383.74
397 fcA = 0.0078 fctA = 47310
398 fcb = 0.9922 fctb = 943
399 fcc = 1.0 fctc = 47110 }
400
401 # Meana-Paneda, Truhlar, Fernandez-Ramos 2011
402 G92f: CH3OH + H -> CH2OH + H2 { A = 1.54E+06 n = 2.35 E = 24.73 }
403 G93f: CH3OH + H -> CH3O + H2 { A = 5.48E+06 n = 2.15 E = 46.44 }
404
405 G94f: CH3OH + O -> CH2OH + OH { A = 3.88E+05 n = 2.50 E = 12.97 }
406 G95f: CH3OH + O -> CH3O + OH { A = 1.30E+05 n = 2.50 E = 20.92 }
407
408 # Zaczek, Lam, Davidson, Hanson 2014 - Total rate
409 # Rasmussen, Wassard et al. 2008 - branching ratios
410 G96f: CH3OH + OH -> CH2OH + H2O { A = 5.14E+04 n = 2.62 E = -2.85 }
411 G97f: CH3OH + OH -> CH3O + H2O { A = 5.71E+03 n = 2.62 E = -2.85 }
412
413 # Peukert & Michael 2013
414 G98f: CH3OH + CH3 -> CH2OH + CH4 { A = 4.90E+12 n = 0.01 E = 63.09 }
415 G99f: CH3OH + CH3 -> CH3O + CH4 { A = 2.31E+13 n = -0.48 E = 61.07 }
416
417 # Klippenstein, Harding, Davis, Tomlin, Skodje 2011
418 G100: CH3OH + O2 -> CH2OH + HO2 { A = 3.58E+05 n = 2.27 E = 178.92 }
419
420 # Alecu & Truhlar 2011
421 G101f: CH3OH + HO2 -> CH2OH + H2O2 { A = 1.62E-04 n = 4.99 E = 44.26 }
422 G102f: CH3OH + HO2 -> CH3O + H2O2 { A = 8.65E-01 n = 3.89 E = 77.04 }
423
424
425 # Acetyl radical
426 # --------------
427
428 G104f: C2H + H + M9 -> C2H2 + M9 { A = 2.60E+33 n = -4.80 E = 7.95
429 Ai= 1.00E+17 ni= -1.00 Ei= .00
430 fcA = 0.3536 fctA = 132
431 fcb = 0.6464 fctb = 1315
432 fcc = 1.0 fctc = 5566 }
433 G105f: C2H + O -> CH + CO { A = 5.00E+13 n = .00 E = .00 }
434 G106f: C2H + OH -> HCCO + H { A = 2.00E+13 n = .00 E = .00 }
435 G107f: C2H + O2 -> HCO + CO { A = 1.00E+13 n = .00 E = -3.16 }
436
437 # Carl, Vereecken & Peeters 2007
438 G108f: C2H + H2 -> C2H2 + H { A = 2.36E+05 n = 2.57 E = 1.08 }
439
440
441 # Ketenyl radical
442 # ---------------
443
444 G109f: HCCO + H -> S-CH2 + CO { A = 1.00E+14 n = .00 E = .00 }
445 G110f: HCCO + CH -> C2H2 + CO { A = 5.00E+13 n = .00 E = .00 }
446 G111f: HCCO + T-CH2 -> C2H3 + CO { A = 3.00E+13 n = .00 E = .00 }
447 G112f: HCCO + CH3 -> C2H4 + CO { A = 5.00E+13 n = .00 E = .00 }
448
449 # Chikan, Leone 2005
450 G113 : HCCO + O -> HCO + CO { A = 7.83E+13 n = .00 E = .00 }
451 G114 : HCCO + O -> CO2 + CH { A = 4.82E+12 n = .00 E = .00 }
452
453 # Mai, Raghunath, Le, Huynh, Nam, Lin 2014
454 # Assumed decomposition of HCOH into HCO+H
455 G115 : HCCO + OH -> CO + HCO + H { A = 2.62E+15 n = -0.41 E = 4.21 }
456 G116f: HCCO + OH -> T-CH2 + CO2 { A = 8.97E+04 n = 2.09 E = -9.19 }
457
458 # Klippenstein, Miller, Harding 2002
459 G117 : HCCO + O2 -> CO2 + CO + H { A = 4.78E+12 n = -0.14 E = 4.81 }
460 G118 : HCCO + O2 -> 2CO + OH { A = 1.91E+11 n = -0.02 E = 4.28 }
461
462
463 # Acetylene
464 # ---------
465
466 # Miller & Klippenstein 2004
467 # Refitted TROE form
468 G119f: C2H2 + H + M9 -> C2H3 + M9 { A = 9.06E+31 n = -4.66 E = 15.82
469 Ai= 1.71E+10 ni= 1.27 Ei= 11.33
470 fcA = 0.751 fctA = 12.1
471 fcb = 0.249 fctb = 10000
472 fcc = 1.0 fctc = 5493 }
473
474 # Nguyen, Vereecken, Peeters 2006 - Total rate
475 # Rajak & Maiti 2010 - Branching ratios
476 G120f: C2H2 + O -> HCCO + H { A = 2.96E+09 n = 1.28 E = 10.34 }
477 G121f: C2H2 + O -> T-CH2 + CO { A = 7.40E+08 n = 1.28 E = 10.34 }
478
479 # Tsang & Hampson 1986
480 # Modified for Collision Limit
481 G122f: C2H + OH -> C2H2 + O { A = 1.81E+13 n = .00 E = .00 }
482
483 # Senosiain, Klippenstein & Miller 2005
484 # HCCOH lumped into CH2CO
485 G123f: C2H2 + OH -> C2H + H2O { A = 2.63E+06 n = 2.14 E = 71.38 }
486 G124f: C2H2 + OH -> CH2CO + H { A = 2.10E+01 n = 3.22 E = -1.76 }
487 G125f: C2H2 + OH -> CH3 + CO { A = 1.28E+09 n = 0.73 E = 10.79 }
488
489 # Laskin & Wang 1999
490 G126f: C2H2 + M9 -> H2C2 + M9 { A = 2.45E+15 n = -0.64 E = 207.94 }
491 G127f: H2C2 + O2 -> 2 HCO { A = 1.00E+13 n = .00 E = .00 }
492
493
494 # Ketene
495 # ------
496 # Updated by Eiteneer & Frenklach 2003
497
498 G128f: CH2CO + H -> HCCO + H2 { A = 5.00E+13 n = .00 E = 33.47 }
499 G129f: CH2CO + O -> HCCO + OH { A = 1.00E+13 n = .00 E = 33.47 }
500 G130f: CH2CO + OH -> HCCO + H2O { A = 7.50E+12 n = .00 E = 8.37 }
501 G131f: CH2CO + T-CH2 -> HCCO + CH3 { A = 3.60E+13 n = .00 E = 46.02 }
502
503 # Woods & Haynes 1994
504 G132f: CH2CO + CH3 -> HCCO + CH4 { A = 7.50E+12 n = .00 E = 54.39 }
505 G133f: CH2CO + CH3 -> C2H5 + CO { A = 9.00E+10 n = .00 E = .00 }
506
507 # Senosiain, Klippenstein & Miller 2006
508 G134f: CH2CO + H -> CH3 + CO { A = 7.77E+08 n = 1.45 E = 11.63 }
509
510 # Lee & Bozzelli 2002
511 G135f: CH2CO + OH -> CH2OH + CO { A = 5.00E+12 n = .00 E = .00 }
512 G136f: CH2CO + T-CH2 -> C2H4 + CO { A = 1.00E+12 n = .00 E = .00 }
513
514 G137f: CH2CO + O -> T-CH2 + CO2 { A = 1.75E+12 n = .00 E = 5.65 }
515
516
517 # Vinyl radical
518 # -------------
519
520 G138f: C2H3 + H + M9 -> C2H4 + M9 { A = 1.40E+30 n = -3.86 E = 13.89
521 Ai= 6.08E+12 ni= 0.27 Ei= 1.17
522 fcA = 0.218 fctA = 207.5
523 fcb = 0.782 fctb = 2663
524 fcc = 1.0 fctc = 6095 }
525 G139f: C2H3 + H -> C2H2 + H2 { A = 3.00E+13 n = .00 E = .00 }
526
527 # Harding, Klippenstein & Georgievskii 2005
528 G140f: C2H3 + O -> CH3 + CO { A = 1.03E+13 n = 0.21 E = -1.79 }
529
530 G141f: C2H3 + OH -> C2H2 + H2O { A = 5.00E+12 n = .00 E = .00 }
531 G142f: C2H3 + O2 -> C2H2 + HO2 { A = 1.34E+06 n = 1.61 E = -1.61 }
532
533 # Stoliarov et al. 2002
534 G143f: C2H3 + CH3 -> C2H2 + CH4 { A = 9.03E+12 n = .00 E = -3.20 }
535
536 # Oguchi, Sato, Matsui 2009
537 # Matsugi, Miyoshi 2014
538 G144f: C2H3 + O2 -> CH2CHO + O { A = 3.80E+11 n = 0.19 E = 0.20 }
539 G145f: C2H3 + O2 -> CH2O + HCO { A = 4.05E+17 n = -1.86 E = 4.88 }
540 G146 : C2H3 + O2 -> CH2O + CO + H { A = 2.22E+16 n = -1.35 E = 3.28 }
541
542 G147f: C2H3 + H2O2 -> C2H4 + HO2 { A = 1.21E+10 n = .00 E = -2.49 }
543 G148f: C2H3 + HCO -> C2H4 + CO { A = 9.00E+13 n = .00 E = .00 }
544
545
546 # CH2CHO
547 # ------
548
549 # Senosiain, Klippenstein & Miller 2006
550 G149f: CH2CHO -> CH2CO + H { A = 1.32E+34 n = -6.57 E = 202.45 }
551 G150f: CH2CHO -> CH3 + CO { A = 6.51E+34 n = -6.87 E = 197.46 }
552
553 # Same as for C2H5 + O
554 G151f: CH2CHO + O -> CH2O + HCO { A = 3.17E+13 n = 0.03 E = -1.65 }
555
556 G152 : CH2CHO + O2 -> CH2O + CO + OH { A = 1.81E+10 n = .00 E = 0.00 }
557 G153 : CH2CHO + O2 -> 2 HCO + OH { A = 2.35E+10 n = .00 E = 0.00 }
558 G154f: CH2CHO + H -> CH2CO + H2 { A = 1.10E+13 n = .00 E = 0.00 }
559 G155f: CH2CHO + OH -> CH2CO + H2O { A = 1.20E+13 n = .00 E = 0.00 }
560
561 G156f: CH2CHO + H -> CH3 + HCO { A = 2.20E+13 n = .00 E = 0.00 }
562 G157f: CH2CHO + OH -> CH2OH + HCO { A = 3.01E+13 n = .00 E = 0.00 }
563 G158f: CH2CHO + CH3 -> C2H5 + HCO { A = 4.90E+14 n = -0.50 E = .00 }
564
565
566 # Acetaldehyde
567 # ------------
568 # Mendes, Zhou, Curran 2014
569 # (O/O2 rates as before/CH2O)
570 # (OH rate from CH2O x 0.5)
571
572 # Sivaramakrishnan, Michael, Klippenstein 2010
573 G159f: CH3CHO + M9 -> CH3 + HCO + M9 { A = 1.63E+59 n =-11.34 E = 401.32
574 Ai= 2.72E+22 ni= -1.74 Ei= 361.33
575 fcA = 0.0 fctA = 1
576 fcb = 0.0 fctb = 1
577 fcc = 0.138 fctc = -670 }
578 G160 : CH3CHO + H -> CH3 + CO + H2 { A = 1.31E+05 n = 2.58 E = 5.10 }
579 G161f: CH3CHO + H -> CH2CHO + H2 { A = 2.72E+03 n = 3.10 E = 21.78 }
580
581 G162 : CH3CHO + O -> CH3 + CO + OH { A = 1.95E+13 n = .00 E = 14.81 }
582 G163 : CH3CHO + OH -> CH3 + CO + H2O { A = 9.70E+05 n = 2.11 E = -7.06 }
583 G164 : CH3CHO + O2 -> CH3 + CO + HO2 { A = 5.00E+13 n = .00 E = 167.36 }
584 G165 : CH3CHO + HO2 -> CH3 + CO + H2O2 { A = 2.78E-03 n = 4.50 E = 20.20 }
585 G166 : CH3CHO + CH3 -> CH3 + CO + CH4 { A = 1.55E+00 n = 3.70 E = 19.10 }
586
587 G167f: CH3CHO + O -> CH2CHO + OH { A = 2.92E+12 n = .00 E = 7.57 }
588 G168f: CH3CHO + OH -> CH2CHO + H2O { A = 6.06E-01 n = 3.90 E = -4.47 }
589 G169f: CH3CHO + HO2 -> CH2CHO + H2O2 { A = 5.43E-02 n = 4.10 E = 78.02 }
590 G170f: CH3CHO + CH3 -> CH2CHO + CH4 { A = 1.44E+00 n = 3.70 E = 37.06 }
591
592
593 # Ethylene
594 # --------
595
596 # Ren, Davidson, Hanson 2012
597 G171 : C2H4 + M9 -> H2C2 + H2 + M9 { A = 3.71E+16 n = .00 E = 283.76 }
598
599 # Miller & Klippenstein 2004
600 # Refitted TROE form
601 G172f: C2H4 + H + M9 -> C2H5 + M9 { A = 2.89E+39 n = -6.64 E = 24.14
602 Ai= 1.37E+09 ni= 1.46 Ei= 5.67
603 fcA = 0.74 fctA = 361.7
604 fcb = 0.26 fctb = 10000
605 fcc = 1.0 fctc = 9096 }
606
607 # Tautermann, Wellenzohn, Clary 2006 (written as reversed)
608 # 10% larger than Huynh, Panasewicz, Ratkiewicz, Truong 2007
609 # Close to the recommendation of Baulch et al. 2005
610 G173f: C2H4 + H -> C2H3 + H2 { A = 1.16E+07 n = 2.23 E = 55.80 }
611
612 # Nguyen, Vereecken, Hou, Nguyen, Peeters 2005
613 G174f: C2H4 + O -> CH2CHO + H { A = 7.66E+09 n = 0.88 E = 4.77 }
614 G175f: C2H4 + O -> T-CH2 + CH2O { A = 7.15E+04 n = 2.47 E = 3.89 }
615 G176f: C2H4 + O -> CH3 + HCO { A = 3.89E+08 n = 1.36 E = 3.71 }
616
617 # Vasu, Hong, Davidson, Hanson, Golden 2010
618 G177f: C2H4 + OH -> C2H3 + H2O { A = 2.23E+04 n = 2.75 E = 9.27 }
619
620 # Wang 2001
621 G178f: C2H4 + O2 -> C2H3 + HO2 { A = 4.22E+13 n = .00 E = 259.83 }
622 G179 : C2H4 + O2 -> CH3 + CO2 + H { A = 4.90E+12 n = 0.42 E = 317.15 }
623
624 # Miller & Klippenstein 2013
625 G180f: C2H4 + CH3 -> C2H3 + CH4 { A = 1.05E+02 n = 3.22 E = 59.86 }
626
627 G181f: C2H4 + CH3 + M9 -> N-C3H7 + M9 { A = 3.00E+63 n = -14.6 E = 76.02
628 Ai= 2.55E+06 ni= 1.60 Ei= 23.85
629 fcA = 0.8106 fctA = 277
630 fcb = 0.1894 fctb = 8748
631 fcc = 1.0 fctc = 7891 }
632
633
634 # Ethyl radical
635 # -------------
636
637 G182f: C2H5 + H + M9 -> C2H6 + M9 { A = 1.99E+41 n = -7.08 E = 27.97
638 Ai= 5.21E+17 ni= -0.99 Ei= 6.61
639 fcA = 0.1578 fctA = 125
640 fcb = 0.8422 fctb = 2219
641 fcc = 1.0 fctc = 6882 }
642
643 G183f: C2H5 + H -> C2H4 + H2 { A = 2.00E+12 n = .00 E = .00 }
644 G184f: C2H5 + OH -> C2H4 + H2O { A = 2.41E+13 n = .00 E = .00 }
645
646 # Miller, Klippenstein & Robertson 2000
647 G185f: C2H5 + O2 -> C2H4 + HO2 { A = 1.92E+07 n = 1.02 E = -8.51 }
648
649 # Zhu, Xu & Lin 2004
650 G186f: C2H5 + CH3 -> C2H4 + CH4 { A = 1.18E+04 n = 2.45 E = 12.22 }
651
652 # Harding, Klippenstein & Georgievskii 2005
653 G187f: C2H5 + O -> CH3 + CH2O { A = 3.17E+13 n = 0.03 E = -1.65 }
654
655 # Ludwig et al. 2006
656 G188f: C2H5 + HO2 -> C2H5O + OH { A = 3.10E+13 n = .00 E = .00 }
657
658 G189f: C2H5 + HCO -> C2H6 + CO { A = 1.20E+14 n = .00 E = .00 }
659 G190f: C2H5 + HO2 -> C2H6 + O2 { A = 3.00E+11 n = .00 E = .00 }
660 G191f: C2H5 + HO2 -> C2H4 + H2O2 { A = 3.00E+11 n = .00 E = .00 }
661
662
663 # Ethoxy radical
664 # --------------
665
666 # Dames 2014
667 G192f: C2H5O + M9 -> CH3 + CH2O + M9 { A = 4.70E+25 n = -3.00 E = 69.17
668 Ai= 6.31E+10 ni= 0.93 Ei= 71.54
669 fcA = 0.574 fctA = 0.3
670 fcb = 0.426 fctb = 2046
671 fcc = 1.0 fctc = 1e5 }
672
673 # Baulch et al. 2005
674 G193f: C2H5O + O2 -> CH3CHO + HO2 { A = 2.29E+10 n = .00 E = 3.66 }
675
676
677 # Ethane
678 # ------
679
680 # Oehlschlaeger et al. 2005
681 G194f: C2H6 + M9 -> 2 CH3 + M9 { A = 3.72E+65 n =-13.14 E = 425.01
682 Ai= 1.88E+50 ni= -9.72 Ei= 449.12
683 fcA = 0.61 fctA = 100
684 fcb = 0.39 fctb = 1900
685 fcc = 1.0 fctc = 6000 }
686
687 # Chakraborty, Zhao, Lin, & Truhlar 2006
688 # Fit 500-2000K
689 G195f: C2H6 + H -> C2H5 + H2 { A = 1.70E+05 n = 2.70 E = 24.02 }
690
691 # Huynh, Zhang, Truong 2008
692 G196f: C2H6 + O -> C2H5 + OH { A = 3.17E+01 n = 3.80 E = 13.10 }
693
694 # Krasnoperov & Michael 2004
695 G197f: C2H6 + OH -> C2H5 + H2O { A = 1.61E+06 n = 2.22 E = 3.10 }
696
697 # Carstensen & Dean 2005
698 G198f: C2H6 + HO2 -> C2H5 + H2O2 { A = 2.61E+02 n = 3.37 E = 66.58 }
699
700 G199f: C2H6 + S-CH2 -> C2H5 + CH3 { A = 4.00E+13 n = .00 E = -2.30 }
701
702 # Peukert, Labbe, Sivaramakrishnan, Michael 2013
703 G200f: C2H6 + CH3 -> C2H5 + CH4 { A = 3.45E+01 n = 3.44 E = 43.47 }
704
705
706 # Propyl radicals
707 # ---------------
708
709
710 # Curran 2006 - HPL
711 G201f: C3H6 + H + M9 -> N-C3H7 + M9 { A = 6.26E+38 n = -6.66 E = 29.29
712 Ai= 2.50E+11 ni= 0.51 Ei= 10.96
713 fcA = 0.0 fctA = 1000
714 fcb = 1.0 fctb = 1310
715 fcc = 1.0 fctc = 48097 }
716 G202f: C3H6 + H + M9 -> I-C3H7 + M9 { A = 8.70E+42 n = -7.50 E = 19.75
717 Ai= 4.24E+11 ni= 0.51 Ei= 5.15
718 fcA = 0.0 fctA = 1000
719 fcb = 1.0 fctb = 645.4
720 fcc = 1.0 fctc = 6844.3 }
721
722 G203f: N-C3H7 + H -> C2H5 + CH3 { A = 3.70E+24 n = -2.92 E = 52.32 }
723 G204f: I-C3H7 + H -> C2H5 + CH3 { A = 1.40E+28 n = -3.94 E = 66.59 }
724 G205f: N-C3H7 + H -> C3H6 + H2 { A = 1.80E+12 n = .00 E = .00 }
725 G206f: I-C3H7 + H -> C3H6 + H2 { A = 3.20E+12 n = .00 E = .00 }
726 G207f: N-C3H7 + O -> C2H5 + CH2O { A = 9.60E+13 n = .00 E = .00 }
727 G208f: I-C3H7 + O -> CH3CHO + CH3 { A = 9.60E+13 n = .00 E = .00 }
728 G209f: N-C3H7 + OH -> C3H6 + H2O { A = 2.41E+13 n = .00 E = .00 }
729 G210f: I-C3H7 + OH -> C3H6 + H2O { A = 2.41E+13 n = .00 E = .00 }
730
731 # DeSain, Miller, Klippenstein & Taatjes 2003
732 G211f: N-C3H7 + O2 -> C3H6 + HO2 { A = 3.70E+16 n = -1.63 E = 14.30 }
733 G212f: I-C3H7 + O2 -> C3H6 + HO2 { A = 6.70E+20 n = -3.02 E = 10.48 }
734
735 # Knyazev & Slagle 2001 - Total rate
736 # Shafir, Slagle & Knyazev 2003 - Branching ratio
737 G213f: N-C3H7 + CH3 -> C3H6 + CH4 { A = 3.31E+12 n = .00 E = -3.22 }
738
739
740 # Propane
741 # -------
742
743 # From Tsang 1988
744 G214f: N-C3H7 + H + M9 -> C3H8 + M9 { A = 4.42E+61 n =-13.55 E = 47.52
745 Ai= 3.61E+13 ni= .00 Ei= .00
746 fcA = 0.685 fctA = 369
747 fcb = 0.315 fctb = 3285
748 fcc = 1.0 fctc = 6667 }
749 G215f: I-C3H7 + H + M9 -> C3H8 + M9 { A = 1.70E+58 n =-12.08 E = 47.13
750 Ai= 2.40E+13 ni= .00 Ei= .00
751 fcA = 0.502 fctA = 1314
752 fcb = 0.498 fctb = 1314
753 fcc = 1.0 fctc = 50000 }
754
755 # Oehlschlaeger et al. 2005
756 G216f: C3H8 + M9 -> C2H5 + CH3 + M9 { A = 5.64E+74 n =-15.74 E = 413.04
757 Ai= 1.29E+37 ni= -5.84 Ei= 407.47
758 fcA = 0.69 fctA = 50
759 fcb = 0.31 fctb = 3000
760 fcc = 1.0 fctc = 9000 }
761 # Carstensen & Dean 2009
762 G217f: C3H8 + H -> N-C3H7 + H2 { A = 9.36E+07 n = 1.97 E = 34.31 }
763 G218f: C3H8 + H -> I-C3H7 + H2 { A = 7.60E+07 n = 1.86 E = 23.43 }
764
765 G219f: C3H8 + O -> N-C3H7 + OH { A = 1.90E+05 n = 2.68 E = 15.55 }
766 G220f: C3H8 + O -> I-C3H7 + OH { A = 4.76E+04 n = 2.71 E = 8.81 }
767
768 # Sivaramkrishnan, Srinivasan, Su, Michael 2009
769 G221f: C3H8 + OH -> N-C3H7 + H2O { A = 5.15E+03 n = 2.94 E = -1.75 }
770 G222f: C3H8 + OH -> I-C3H7 + H2O { A = 1.81E+05 n = 2.44 E = -2.24 }
771
772 G223f: C3H8 + CH3 -> N-C3H7 + CH4 { A = 9.03E-01 n = 3.65 E = 29.93 }
773 G224f: C3H8 + CH3 -> I-C3H7 + CH4 { A = 1.51E+00 n = 3.46 E = 29.93 }
774 G225f: C3H8 + HO2 -> N-C3H7 + H2O2 { A = 4.76E+04 n = 2.55 E = 69.00 }
775 G226f: C3H8 + HO2 -> I-C3H7 + H2O2 { A = 9.63E+03 n = 2.60 E = 58.20 }
776
777
778
779 #=========================================================================#
780 # #
781 # "Experimental and Modeling Study of Shock-Tube Oxidation of Acetylene" #
782 # B. Eiteneer and M. Frenklach #
783 # Int. J. Chem. Kinet. 35, 391:414 (2003) #
784 # #
785 #=========================================================================#
786
787
788 # Propynylidene
789 # -------------
790
791 # Nguyen, Mebel, Lin, Kaiser 2001
792 # Loison, Bergeat 2008 (reduced to collision rate)
793 R004f: C2H2 + CH -> C3H2 + H { A = 1.89E+14 n = .00 E = .00 }
794
795 # Boullart, Devriendt, Borns, Peeters 1996
796 R005f: C3H2 + O -> C2H + HCO { A = 1.36E+14 n = .00 E = .00 }
797
798 R006f: C3H2 + OH -> C2H2 + HCO { A = 1.00E+13 n = .00 E = .00 }
799 R007f: C3H2 + O2 -> HCCO + CO + H { A = 1.25E+11 n = .00 E = 4.18 }
800 R008f: C3H2 + CH -> C4H2 + H { A = 5.00E+13 n = .00 E = .00 }
801 R009f: C3H2 + T-CH2 -> N-C4H3 + H { A = 5.00E+13 n = .00 E = .00 }
802 R010f: C3H2 + CH3 -> C4H4 + H { A = 5.00E+12 n = .00 E = .00 }
803 R011f: C3H2 + HCCO -> N-C4H3 + CO { A = 1.00E+13 n = .00 E = .00 }
804
805
806 # Propynal
807 # --------
808
809 # Estimated
810 R012f: C2H + HCO -> C3H2O { A = 5.00E+13 n = .00 E = .00 }
811 # From P-C3H4 + H
812 R013f: C3H2O + H -> C2H2 + HCO { A = 3.46E+12 n = 0.44 E = 22.86 }
813
814 # Taken from CH3CHO
815 R014 : C3H2O + H -> C2H + CO + H2 { A = 1.31E+05 n = 2.58 E = 5.10 }
816 R015 : C3H2O + O -> C2H + CO + OH { A = 1.95E+13 n = .00 E = 14.81 }
817 R016 : C3H2O + OH -> C2H + CO + H2O { A = 9.10E+05 n = 2.11 E = -7.06 }
818 R017 : C3H2O + O2 -> C2H + CO + HO2 { A = 5.00E+13 n = .00 E = 167.36 }
819 R018 : C3H2O + HO2 -> C2H + CO + H2O2 { A = 2.78E-03 n = 4.50 E = 20.20 }
820 R019 : C3H2O + CH3 -> C2H + CO + CH4 { A = 1.55E+00 n = 3.70 E = 19.10 }
821
822
823 # Propargyl radical
824 # -----------------
825
826 R020f: C2H2 + HCCO -> C3H3 + CO { A = 1.00E+11 n = .00 E = 12.55 }
827
828 # Tsang & Hampson 1986
829 R021f: C2H + CH3 -> C3H3 + H { A = 2.41E+13 n = .00 E = .00 }
830
831 # Polino, Klippenstein, Harding, Georgievskii 2013
832 R022f: C2H2 + S-CH2 -> C3H3 + H { A = 3.97E+15 n = -0.57 E = -0.02 }
833
834 # 2x rate for C2H3+H
835 R023f: C3H2 + H + M9 -> C3H3 + M9 { A = 2.80E+30 n = -3.86 E = 13.89
836 Ai= 1.02E+13 ni= .27 Ei= 1.17
837 fcA = 0.218 fctA = 207.5
838 fcb = 0.782 fctb = 2663
839 fcc = 1.0 fctc = 6095 }
840
841 # Miller & Klippenstein 2003 (1bar)
842 R024f: C3H3 + H -> C3H2 + H2 { A = 1.10E+10 n = 1.13 E = 58.28 }
843
844 # Adapted from C2H2 + OH
845 R025f: C3H3 + OH -> C2H3CHO { A = 2.10E+01 n = 3.22 E = -1.76 }
846 R026f: C3H3 + OH -> C2H4 + CO { A = 1.28E+09 n = 0.73 E = 10.79 }
847
848 # 1/2 rate for C2H4+OH
849 R027f: C3H3 + OH -> C3H2 + H2O { A = 1.13E+05 n = 2.28 E = 10.32 }
850
851 # Lee, Nam & Choi 2006
852 # Kwon, Nam, Youn, Joo, Lee, & Choi 2006
853 # Slagle, Gmurczyk, Batt & Gutman 1991
854 R029f: C3H3 + O -> C3H2O + H { A = 1.38E+14 n = .00 E = .00 }
855
856 # Hahn, Klippenstein, Miller 2001
857 R030f: C3H3 + O2 -> CH2CO + HCO { A = 1.70E+05 n = 1.70 E = 6.28 }
858
859 R031 : C3H3 + HO2 -> C2H3 + CO + OH { A = 8.00E+11 n = .00 E = .00 }
860
861 # Wang 2001
862 R032f: C3H3 + HO2 -> A-C3H4 + O2 { A = 3.00E+11 n = .00 E = .00 }
863 R033f: C3H3 + HO2 -> P-C3H4 + O2 { A = 3.00E+11 n = .00 E = .00 }
864 R034f: P-C3H4 + O2 -> CH3 + HCO + CO { A = 4.00E+14 n = .00 E = 175.43 }
865
866 R035f: C3H3 + HCO -> A-C3H4 + CO { A = 2.50E+13 n = .00 E = .00 }
867 R036f: C3H3 + HCO -> P-C3H4 + CO { A = 2.50E+13 n = .00 E = .00 }
868 R037f: C3H3 + CH -> I-C4H3 + H { A = 5.00E+13 n = .00 E = .00 }
869
870 # Miller, Melius 1992
871 R038f: C3H3 + T-CH2 -> C4H4 + H { A = 5.00E+13 n = .00 E = .00 }
872
873
874 # Allene
875 # ------
876
877 # Thiesemann, Clifford, Taatjes, Klippenstein 2001
878 # Zhang, Maksyutenko, Kaiser 2012
879 R039f: C2H4 + CH -> A-C3H4 + H { A = 9.98E+14 n = -0.31 E = .00 }
880
881 # Miller, Senosiain, Klippenstein, Georgievskii 2008
882 # Refitted 800K-2500K - 1bar
883 R041f: A-C3H4 + H -> C2H2 + CH3 { A = 8.95E+13 n = -0.02 E = 47.07 }
884 R042f: A-C3H4 + H -> A-C3H5 { A = 2.01E+49 n =-10.77 E = 82.10 }
885 R043f: A-C3H4 + H -> T-C3H5 { A = 6.70E+42 n =-12.46 E = 68.45 }
886
887 # Giri, Fernandes, Bentz, Hippler, Olzmann 2011
888 R040f: A-C3H4 + M0 -> C3H3 + H + M0 { A = 2.15E+43 n = -6.81 E = 420.61 }
889
890 # Same as for C2H4
891 R044f: A-C3H4 + H -> C3H3 + H2 { A = 1.33E+06 n = 2.53 E = 51.21 }
892 R045f: A-C3H4 + OH -> C3H3 + H2O { A = 1.31E-01 n = 4.20 E = -3.60 }
893 R046f: A-C3H4 + CH3 -> C3H3 + CH4 { A = 1.05E+02 n = 3.22 E = 59.86 }
894 R047f: A-C3H4 + HO2 -> C3H3 + H2O2 { A = 9.76E+10 n = 0.12 E = 97.78 }
895
896 # Nguyen, Peeters & Vereecken 2006 - rate
897 # Leonori, Balucani et al. 2012 - products
898 R048f: A-C3H4 + O -> C2H4 + CO { A = 9.63E+06 n = 2.05 E = 0.75 }
899
900 # Liu, Maluc, Jonah 1988
901 R049f: A-C3H4 + OH -> CH2CO + CH3 { A = 4.03E+12 n = .00 E = -0.83 }
902
903
904 # Propyne
905 # -------
906
907 # Miller & Klippenstein 2003 (1bar)
908 R050f: A-C3H4 -> P-C3H4 { A = 7.76E+39 n = -7.80 E = 328.22 }
909
910 # Sheen, Rosado-Reyes, Tsang 2013
911 R051f: C2H2 + CH3 -> P-C3H4 + H { A = 1.48E+11 n = 0.60 E = 59.86 }
912 R052f: P-C3H4 + H -> A-C3H4 + H { A = 1.58E+18 n = -1.00 E = 50.72 }
913
914 # Miller, Senosiain, Klippenstein, Georgievskii 2008 - P=1bar
915 R053f: P-C3H4 + H -> T-C3H5 { A = 8.83E+52 n =-12.36 E = 68.81 }
916 R054f: P-C3H4 + H -> S-C3H5 { A = 1.53E+49 n =-11.97 E = 59.18 }
917
918 # Giri, Fernandes, Bentz, Hippler, Olzmann 2011
919 R055f: P-C3H4 + M0 -> C3H3 + H + M0 { A = 2.15E+43 n = -6.81 E = 420.61 }
920
921 # 1/2 the rate for C2H6
922 R056f: P-C3H4 + H -> C3H3 + H2 { A = 8.50E+04 n = 2.70 E = 24.02 }
923 R057f: P-C3H4 + O -> C3H3 + OH { A = 1.59E+01 n = 3.80 E = 13.10 }
924 R058f: P-C3H4 + OH -> C3H3 + H2O { A = 8.05E+05 n = 2.22 E = 3.10 }
925 R059f: P-C3H4 + CH3 -> C3H3 + CH4 { A = 1.73E+01 n = 3.44 E = 43.47 }
926 R060f: P-C3H4 + HO2 -> C3H3 + H2O2 { A = 1.30E+02 n = 3.37 E = 66.58 }
927
928 # Adapted from C2H2+O (half-half)
929 # Zhao, Wu, Zhao et al. 2009 - Products (singlet)
930 # Balucani, Leonori et al. 2014 - Products (triplet)
931 R061f: P-C3H4 + O -> C2H4 + CO { A = 1.85E+09 n = 1.28 E = 10.34 }
932 R062f: P-C3H4 + O -> HCCO + CH3 { A = 1.85E+09 n = 1.28 E = 10.34 }
933
934 # From C2H2 + OH
935 R063f: P-C3H4 + OH -> CH2CO + CH3 { A = 2.10E+01 n = 3.22 E = -1.76 }
936 R064f: P-C3H4 + OH -> C2H5 + CO { A = 1.28E+09 n = 0.73 E = 10.79 }
937
938
939 # Propenal
940 # --------
941
942 R065f: C2H3 + HCO -> C2H3CHO { A = 1.80E+13 n = .00 E = .00 }
943
944 # Baulch et al. 2005 - adapted from CH3CHO
945 R066 : C2H3CHO + H -> C2H3 + CO + H2 { A = 1.31E+05 n = 2.58 E = 5.10 }
946 R067 : C2H3CHO + O -> C2H3 + CO + OH { A = 1.95E+13 n = .00 E = 14.81 }
947 R068 : C2H3CHO + OH -> C2H3 + CO + H2O { A = 9.70E+05 n = 2.11 E = -7.06 }
948 R069 : C2H3CHO + HO2 -> C2H3 + CO + H2O2 { A = 2.78E-03 n = 4.50 E = 20.20 }
949 R070 : C2H3CHO + CH3 -> C2H3 + CO + CH4 { A = 1.55E+00 n = 3.70 E = 10.10 }
950
951
952 # Allyl radical
953 # -------------
954
955 # Stoliarov et al. 2002 - 1.33bar
956 R071f: C2H3 + CH3 -> A-C3H5 + H { A = 1.93E+18 n = -1.25 E = 32.09 }
957
958 # Klippenstein, Harding, Georgievskii, Miller 2008
959 # Fitted 400K-2500K
960 R072f: A-C3H5 + H -> A-C3H4 + H2 { A = 9.56E+03 n = 2.80 E = 13.77 }
961
962 # Tsang 1991
963 R073f: A-C3H5 + OH -> A-C3H4 + H2O { A = 6.03E+12 n = .00 E = .00 }
964 R074f: A-C3H5 + CH3 -> A-C3H4 + CH4 { A = 3.01E+12 n = -0.32 E = -0.55 }
965 R075f: A-C3H5 + C2H3 -> A-C3H4 + C2H4 { A = 2.41E+12 n = .00 E = .00 }
966 R076f: A-C3H5 + C2H5 -> A-C3H4 + C2H6 { A = 9.64E+11 n = .00 E = -0.55 }
967
968 # Lynch, Annesley, Aul, Yang, Tranter 2013
969 R077f: A-C3H5 + A-C3H5 -> A-C3H4 + C3H6 { A = 7.50E+11 n = .00 E = .00 }
970
971 # Hoyermann, et al. 2009 - equipartition
972 # Rate revised based on updated C2H5+O
973 R078f: A-C3H5 + O -> C2H3CHO + H { A = 1.69E+13 n = 0.03 E = -1.65 }
974 R079 : A-C3H5 + O -> C2H4 + CO + H { A = 1.69E+13 n = 0.03 E = -1.65 }
975
976 # Lee & Bozzelli 2005
977 R080f: A-C3H5 + O2 -> A-C3H4 + HO2 { A = 2.06E+04 n = 2.19 E = 73.60 }
978 R081f: A-C3H5 + O2 -> C2H3CHO + OH { A = 3.36E+05 n = 1.81 E = 80.29 }
979 R082 : A-C3H5 + O2 -> C2H2 + CH2O + OH { A = 9.71E+20 n = -2.70 E = 104.52 }
980 R083f: A-C3H5 + O2 -> CH2CHO + CH2O { A = 3.08E+09 n = 0.37 E = 70.75 }
981
982 # From A1CH2+HO2
983 R084f: A-C3H5 + HO2 -> C3H5O + OH { A = 1.19E+09 n = 1.03 E = -9.41 }
984
985
986 # Propen-2-yl radical
987 # -------------------
988
989 # From C2H3
990 R085f: T-C3H5 + H -> P-C3H4 + H2 { A = 3.00E+13 n = .00 E = .00 }
991 R086f: T-C3H5 + OH -> P-C3H4 + H2O { A = 5.00E+12 n = .00 E = .00 }
992 R087f: T-C3H5 + O2 -> P-C3H4 + HO2 { A = 1.34E+06 n = 1.61 E = -1.61 }
993 R088f: T-C3H5 + CH3 -> P-C3H4 + CH4 { A = 9.03E+12 n = .00 E = -3.20 }
994
995 # From C2H5
996 R089f: T-C3H5 + H -> A-C3H4 + H2 { A = 2.00E+12 n = .00 E = .00 }
997 R090f: T-C3H5 + OH -> A-C3H4 + H2O { A = 2.41E+13 n = .00 E = .00 }
998 R091f: T-C3H5 + O2 -> A-C3H4 + HO2 { A = 1.92E+07 n = 1.02 E = -8.51 }
999 R092f: T-C3H5 + CH3 -> A-C3H4 + CH4 { A = 1.18E+04 n = 2.45 E = 12.22 }
1000
1001 R093f: T-C3H5 + O -> CH2CO + CH3 { A = 6.00E+13 n = .00 E = .00 }
1002 R094 : T-C3H5 + HO2 -> CH2CO + CH3 + OH { A = 2.00E+13 n = .00 E = .00 }
1003
1004 # Adapted from C2H3+O2 (both reactions lumped)
1005 R095 : T-C3H5 + O2 -> CH2O + CH3 + CO { A = 8.72E+16 n = -1.49 E = 3.66 }
1006
1007
1008 # Propen-1-yl radical
1009 # -------------------
1010 # From C2H3
1011
1012 # Miller, Senosiain, Klippenstein, Georgievskii 2008
1013 # Refitted 800K-2500K - P=1bar
1014 R096f: C2H2 + CH3 -> S-C3H5 { A = 7.45E+43 n =-10.13 E = 77.50 }
1015
1016 R097f: S-C3H5 + H -> P-C3H4 + H2 { A = 1.50E+13 n = .00 E = .00 }
1017 R098f: S-C3H5 + OH -> P-C3H4 + H2O { A = 2.50E+12 n = .00 E = .00 }
1018 R099f: S-C3H5 + O2 -> P-C3H4 + HO2 { A = 6.70E+05 n = 1.61 E = -1.61 }
1019 R100f: S-C3H5 + CH3 -> P-C3H4 + CH4 { A = 4.52E+12 n = .00 E = -3.20 }
1020
1021 R101f: S-C3H5 + O -> C2H5 + CO { A = 6.00E+13 n = .00 E = .00 }
1022 R102 : S-C3H5 + HO2 -> C2H5 + CO + OH { A = 2.00E+13 n = .00 E = .00 }
1023
1024 R103f: S-C3H5 + O2 -> CH3CHO + HCO { A = 4.05E+17 n = -1.86 E = 4.88 }
1025 R104f: S-C3H5 + O2 -> CH3CHO + CO + H { A = 2.22E+16 n = -1.35 E = 3.28 }
1026
1027
1028 # Propanone
1029 # ---------
1030
1031 # NC7 path from LLNL
1032 R105f: C3H5O -> C2H3CHO + H { A = 1.00E+14 n = .00 E = 121.75 }
1033 R106f: C3H5O -> C2H3 + CH2O { A = 2.03E+12 n = 0.09 E = 98.58 }
1034 R107f: C3H5O + O2 -> C2H3CHO + HO2 { A = 1.00E+12 n = .00 E = 25.10 }
1035
1036
1037 # Propene
1038 # -------
1039
1040 # High pressure limit (backward rate)
1041 # -> Harding, Klippenstein, & Georgievskii 2007
1042 # Fall-off
1043 # -> Hung, Tsai, Matsui, Wang, Miyoshi 2015 (1atm)
1044 # -> Stoliarov et al. 2002 (20% higher)
1045 R108f: C3H6 -> A-C3H5 + H { A = 3.87E+57 n =-12.22 E = 476.14 }
1046 R109f: C3H6 -> C2H3 + CH3 { A = 9.20E+70 n =-15.96 E = 537.86 }
1047 R110f: C3H6 -> H2C2 + CH4 { A = 4.61E+68 n =-15.76 E = 522.21 }
1048
1049 # Miller & Klippenstein 2013
1050 # Refitted at P=1bar
1051 R114f: C3H6 + H -> C2H4 + CH3 { A = 2.67E+12 n = 0.47 E = 22.73 }
1052 R115f: C3H6 + H -> A-C3H5 + H2 { A = 6.03E+05 n = 2.39 E = 18.79 }
1053 R116f: C3H6 + H -> S-C3H5 + H2 { A = 8.58E+02 n = 3.25 E = 50.90 }
1054 R117f: C3H6 + H -> T-C3H5 + H2 { A = 1.49E+02 n = 3.38 E = 37.28 }
1055
1056 # Vasu, Hong, Davidson, Hanson 2010
1057 # Badra, Khaled, Raj Giri, Farooq 2015
1058 R118f: C3H6 + OH -> A-C3H5 + H2O { A = 4.19E+13 n = .00 E = 19.46 }
1059 R119f: C3H6 + OH -> S-C3H5 + H2O { A = 1.67E+13 n = .00 E = 18.87 }
1060 R120f: C3H6 + OH -> T-C3H5 + H2O { A = 4.33E+12 n = .00 E = 18.97 }
1061
1062 # Cavallotti, Leonori, Balucani et al. 2014
1063 # CH3CH replaced by C2H4 - 1bar
1064 R121f: C3H6 + O -> CH2CHO + CH3 { A = 8.12E+08 n = 1.25 E = 2.26 }
1065 R122f: C3H6 + O -> C2H4 + CH2O { A = 3.63E+10 n = 0.82 E = 7.65 }
1066 R123f: C3H6 + O -> A-C3H5 + OH { A = 1.43E+02 n = 3.37 E = 0.73 }
1067
1068 # Rate from C3H8 + X (x0.5)
1069 R124f: C3H6 + HO2 -> A-C3H5 + H2O2 { A = 2.38E+04 n = 2.55 E = 69.00 }
1070 R125f: C3H6 + CH3 -> A-C3H5 + CH4 { A = 4.57E-01 n = 3.65 E = 29.93 }
1071
1072 # From C2H4
1073 R126f: C3H6 + CH3 -> S-C3H5 + CH4 { A = 5.25E+01 n = 3.22 E = 59.86 }
1074 R127f: C3H6 + CH3 -> T-C3H5 + CH4 { A = 2.63E+01 n = 3.22 E = 47.31 }
1075
1076
1077
1078 #==========================================================================#
1079 # #
1080 # "Shock-Tube and Modeling Study of Diacetylene Pyrolysis and Oxidation" #
1081 # Y. Hidaka, Y. Henmi, T. Ohonishi & T. Okuno #
1082 # Combustion and Flame 130:62-82 (2002) #
1083 # #
1084 #==========================================================================#
1085
1086 # Diacetylene
1087 # -----------
1088
1089 # From C2H
1090 H01 : C4H + O2 -> C2H + 2CO { A = 1.00E+13 n = .00 E = -3.16 }
1091
1092 H02f: C4H2 -> C4H + H { A = 2.20E+14 n = .00 E = 487.85 }
1093 H03f: C4H2 + H -> C4H + H2 { A = 2.00E+14 n = .00 E = 108.78 }
1094
1095 # Ceursters, Nguyen, Peeters, Nguyen 2000
1096 H04f: C2H2 + C2H -> C4H2 + H { A = 7.80E+13 n = .00 E = .00 }
1097
1098 # Klippenstein & Miller 2005
1099 # Refitted Rate & TROE form
1100 H05f: C4H2 + H + M9 -> I-C4H3 + M9 { Ai= 4.31E+10 ni= 1.16 Ei= 7.33
1101 A = 2.30E+45 n = -8.10 E = 10.49
1102 fcA = 0.901 fctA = 12.5
1103 fcB = 0.099 fctB = 10000
1104 fcc = 1.0 fctc = 6674 }
1105 H06f: C4H2 + H -> N-C4H3 { A = 1.37E+39 n = -7.87 E = 64.61 }
1106
1107 H07f: C4H2 + O -> C3H2 + CO { A = 2.80E+13 n = .00 E = 7.24 }
1108 H08f: C4H2 + O -> C4H2O { A = 4.00E+13 n = .00 E = .00 }
1109 H09f: C4H2 + O2 -> HCCO + HCCO { A = 9.56E+12 n = .00 E = 130.12 }
1110
1111 # Senosiain, Klippenstein & Miller 2007
1112 H10f: C4H2 + OH -> C4H + H2O { A = 9.15E+09 n = 1.03 E = 90.99 }
1113 H11f: C4H2 + OH -> C4H2O + H { A = 3.41E+10 n = 0.31 E = 5.00 }
1114 H12f: C4H2 + OH -> C3H3 + CO { A = 2.11E+23 n = -3.47 E = 31.76 }
1115
1116
1117 # Ethynylketene
1118 # -------------
1119
1120 H13f: C4H2O + H -> C2H2 + HCCO { A = 5.00E+13 n = .00 E = 12.55 }
1121 H14f: C4H2O + O -> C3H2 + CO2 { A = 1.00E+13 n = .00 E = .00 }
1122 H15f: C4H2O + OH -> CH2CO + HCCO { A = 1.00E+07 n = 2.00 E = 8.37 }
1123
1124
1125 # C4H3 radicals
1126 # -------------
1127
1128 # Wang 1992 ??
1129 H16f: N-C4H3 -> I-C4H3 { A = 4.10E+43 n = -9.50 E = 221.75 }
1130 H17f: N-C4H3 + H -> I-C4H3 + H { A = 2.50E+20 n = -1.67 E = 45.19 }
1131 H18f: N-C4H3 + H -> C4H4 { A = 2.00E+47 n =-10.26 E = 54.69 }
1132 H19f: I-C4H3 + H -> C4H4 { A = 3.40E+43 n = -9.01 E = 50.71 }
1133 H20f: N-C4H3 + H -> C2H2 + H2C2 { A = 6.30E+25 n = -3.34 E = 41.90 }
1134 H21f: I-C4H3 + H -> C2H2 + H2C2 { A = 2.80E+23 n = -2.55 E = 45.10 }
1135
1136 # From C2H3
1137 H22f: N-C4H3 + H -> C4H2 + H2 { A = 1.50E+13 n = .00 E = .00 }
1138 H23f: I-C4H3 + H -> C4H2 + H2 { A = 3.00E+13 n = .00 E = .00 }
1139 H24f: N-C4H3 + OH -> C4H2 + H2O { A = 2.50E+12 n = .00 E = .00 }
1140 H25f: I-C4H3 + OH -> C4H2 + H2O { A = 5.00E+12 n = .00 E = .00 }
1141 H26f: N-C4H3 + O2 -> C4H2 + HO2 { A = 6.70E+05 n = 1.61 E = -1.61 }
1142 H27f: I-C4H3 + O2 -> C4H2 + HO2 { A = 1.34E+06 n = 1.61 E = -1.61 }
1143
1144 H28f: N-C4H3 + O -> C2H2 + HCCO { A = 1.03E+13 n = 0.21 E = -1.79 }
1145 H29f: I-C4H3 + O -> CH2CO + C2H { A = 2.00E+13 n = .00 E = .00 }
1146 H30f: I-C4H3 + O2 -> HCCO + CH2CO { A = 1.63E+11 n = .00 E = -7.53 }
1147
1148
1149 # Vinylacetylene
1150 # --------------
1151
1152 H31f: C4H4 -> C4H2 + H2 { A = 1.30E+15 n = .00 E = 396.14 }
1153 H32f: C4H4 -> C2H2 + C2H2 { A = 3.40E+13 n = .00 E = 322.59 }
1154
1155 # Decomposition of C4H4 revisited
1156 # Problem for diffusion flamelets with C2H2+H2C2
1157 #H30f: C2H3 + C2H -> C4H4 { A = 1.00E+14 n = .00 E = .00 }
1158 #H31f: C2H4 + C2H -> C4H4 + H { A = 1.20E+13 n = .00 E = .00 }
1159
1160 # Miller, Klippenstein & Robertson 2000
1161 H33f: C2H3 + C2H2 -> C4H4 + H { A = 1.32E+12 n = 0.16 E = 34.78 }
1162
1163 # Adapted from C2H4 - 3kcal
1164 H34f: C4H4 + H -> N-C4H3 + H2 { A = 1.16E+07 n = 2.23 E = 55.80 }
1165 H35f: C4H4 + H -> I-C4H3 + H2 { A = 5.80E+06 n = 2.23 E = 43.25 }
1166 H36f: C4H4 + OH -> N-C4H3 + H2O { A = 2.23E+04 n = 2.75 E = 9.27 }
1167 H37f: C4H4 + OH -> I-C4H3 + H2O { A = 1.12E+04 n = 2.75 E = -3.28 }
1168 H38f: C4H4 + CH3 -> N-C4H3 + CH4 { A = 5.25E+01 n = 3.22 E = 59.86 }
1169 H39f: C4H4 + CH3 -> I-C4H3 + CH4 { A = 2.63E+01 n = 3.22 E = 47.31 }
1170
1171 # From C2H4
1172 H40f: C4H4 + O -> C3H3 + HCO { A = 6.00E+08 n = 1.45 E = -3.60 }
1173
1174 # From C2H2
1175 #41f: C4H4 + OH -> CH2CO + C2H3 { A = 2.10E+01 n = 3.22 E = -1.76 }
1176 H42f: C4H4 + OH -> A-C3H5 + CO { A = 1.28E+09 n = 0.73 E = 10.79 }
1177
1178
1179 # Hexatriyne & Octotetrayne
1180 # -------------------------
1181
1182 # Reactions of C6H2 & C8H2
1183 # Ceursters, Nguyen, Peeters, Nguyen 2000
1184 H43f: C4H2 + C2H -> C6H2 + H { A = 7.80E+13 n = .00 E = .00 }
1185 H44f: C2H2 + C4H -> C6H2 + H { A = 7.80E+13 n = .00 E = .00 }
1186 H45f: C6H2 + C2H -> C8H2 + H { A = 7.80E+13 n = .00 E = .00 }
1187 H46f: C4H2 + C4H -> C8H2 + H { A = 7.80E+13 n = .00 E = .00 }
1188
1189 # Estimated
1190 H47f: C4H + C4H -> C8H2 { A = 1.00E+14 n = .00 E = .00 }
1191
1192 # From C4H2 + OH
1193 H48 : C6H2 + OH -> C4H2 + HCCO { A = 3.41E+10 n = 0.31 E = 5.00 }
1194 H49 : C8H2 + OH -> C6H2 + HCCO { A = 3.41E+10 n = 0.31 E = 5.00 }
1195
1196
1197
1198 #==========================================================================#
1199 # #
1200 # "Detailed kinetic modelling of butadiene Oxidation at high temperatures" #
1201 # A. Laskin, H. Wang, C. Law. #
1202 # Int. J. Chem. Kinet. 2000. 32-589 #
1203 # #
1204 #==========================================================================#
1205
1206
1207 # 1,3-Butadiene
1208 # -------------
1209
1210 # Peukert, Naumann, Braun-unkhoff 2009
1211 B01f: C4H6 -> C2H4 + C2H2 { A = 7.00E+12 n = .00 E = 280.75 }
1212
1213 B02f: C2H3 + C2H3 -> C4H6 { A = 1.50E+42 n = -8.84 E = 52.23 }
1214
1215 # Ismail, Georgievskii, Taatjes, et al. 2007
1216 # Rate fitted at 1.33bar
1217 B03f: C2H4 + C2H3 -> C4H6 + H { A = 2.15E+12 n = 0.46 E = 62.65 }
1218
1219 B04f: C3H6 + C2H3 -> C4H6 + CH3 { A = 7.23E+11 n = .00 E = 20.92 }
1220
1221 #B05f: C4H6 + H -> P-C3H4 + CH3 { A = 2.00E+12 n = .00 E = 29.29 }
1222 #B06f: C4H6 + H -> A-C3H4 + CH3 { A = 2.00E+12 n = .00 E = 29.29 }
1223
1224 B07f: C4H6 -> I-C4H5 + H { A = 5.70E+36 n = -6.27 E = 470.09 }
1225 B08f: C4H6 -> N-C4H5 + H { A = 5.30E+44 n = -8.62 E = 517.18 }
1226 B09f: C4H6 -> C4H4 + H2 { A = 2.50E+15 n = .00 E = 396.22 }
1227
1228 # Adapted from C2H4
1229 # Rate for OH from Vasu, Hanson, et al. 2010 - refitted
1230 # Rate for O refitted - 8e11 backward
1231 B10f: C4H6 + H -> N-C4H5 + H2 { A = 1.16E+07 n = 2.23 E = 55.80 }
1232 B11f: C4H6 + O -> N-C4H5 + OH { A = 7.12E+14 n = -0.23 E = 41.03 }
1233 B12f: C4H6 + OH -> N-C4H5 + H2O { A = 1.56E+05 n = 2.46 E = 7.78 }
1234 B13f: C4H6 + O2 -> N-C4H5 + HO2 { A = 4.22E+13 n = .00 E = 259.83 }
1235 B14f: C4H6 + CH3 -> N-C4H5 + CH4 { A = 1.05E+02 n = 3.22 E = 59.86 }
1236 B15f: C4H6 + HO2 -> N-C4H5 + H2O2 { A = 1.66E+10 n = 0.36 E = 95.13 }
1237
1238 # Adapted from C2H4 - 3kcal
1239 B16f: C4H6 + H -> I-C4H5 + H2 { A = 5.80E+06 n = 2.23 E = 43.25 }
1240 B17f: C4H6 + O -> I-C4H5 + OH { A = 3.56E+14 n = -0.23 E = 28.48 }
1241 B18f: C4H6 + OH -> I-C4H5 + H2O { A = 2.17E+06 n = 2.08 E = 6.58 }
1242 B19f: C4H6 + O2 -> I-C4H5 + HO2 { A = 2.11E+13 n = .00 E = 247.28 }
1243 B20f: C4H6 + CH3 -> I-C4H5 + CH4 { A = 5.25E+01 n = 3.22 E = 47.31 }
1244 B21f: C4H6 + HO2 -> I-C4H5 + H2O2 { A = 8.31E+09 n = 0.36 E = 82.58 }
1245
1246 # From C3H6 + O (x2)
1247 # Cavallotti, Leonori, Balucani et al. 2014
1248 B22f: C4H6 + O -> CH2CHO + C2H3 { A = 1.62E+09 n = 1.25 E = 2.26 }
1249 B23f: C4H6 + O -> A-C3H4 + CH2O { A = 7.26E+10 n = 0.82 E = 7.65 }
1250
1251 # From C2H4+O2
1252 B25 : C4H6 + O2 -> A-C3H5 + CO2 + H { A = 4.90E+12 n = 0.42 E = 317.15 }
1253
1254
1255 # 1,2-Butadiene
1256 # -------------
1257
1258 B26f: D-C4H6 -> C4H6 { A = 3.00E+13 n = .00 E = 271.96 }
1259 B27f: D-C4H6 + H -> C4H6 + H { A = 2.00E+13 n = .00 E = 16.74 }
1260
1261 # HPL from Knyazev & Slagle 2001
1262 B28f: C3H3 + CH3 + M9 -> D-C4H6 + M9 { A = 2.60E+57 n =-11.94 E = 40.89
1263 Ai= 4.09E+13 ni= .00 Ei= -1.08
1264 fcA = 0.825 fctA = 1341
1265 fcb = 0.175 fctb = 60000
1266 fcc = 1.0 fctc = 9770 }
1267
1268 # Revised using C3H6+H->C2H4+CH3
1269 B29f: D-C4H6 + H -> A-C3H4 + CH3 { A = 2.67E+12 n = 0.47 E = 22.72 }
1270 # Revised using A-C3H4+H->P-C3H4+H
1271 B30f: D-C4H6 + H -> P-C3H4 + CH3 { A = 2.55E+18 n = -1.09 E = 47.84 }
1272
1273 # Revised based on C3H6+X->A-C3H5
1274 B31f: D-C4H6 -> I-C4H5 + H { A = 1.91E+54 n =-11.28 E = 464.83 }
1275 B32f: D-C4H6 + H -> I-C4H5 + H2 { A = 6.03E+05 n = 2.39 E = 18.79 }
1276 B33f: D-C4H6 + O -> I-C4H5 + OH { A = 1.43E+02 n = 3.37 E = 0.73 }
1277 B34f: D-C4H6 + OH -> I-C4H5 + H2O { A = 4.19E+13 n = .00 E = 19.46 }
1278 B35f: D-C4H6 + O2 -> I-C4H5 + HO2 { A = 1.17E+12 n = 0.41 E = 162.33 }
1279 B36f: D-C4H6 + CH3 -> I-C4H5 + CH4 { A = 4.57E-01 n = 3.65 E = 29.93 }
1280
1281 # From C3H6+X->T-C3H5
1282 #B37f: D-C4H6 + M0 -> S-C4H5 + H + M0 { A = 5.38E+42 n = -6.81 E = 420.61 }
1283 B38f: D-C4H6 + H -> S-C4H5 + H2 { A = 1.49E+02 n = 3.38 E = 37.28 }
1284 B39f: D-C4H6 + OH -> S-C4H5 + H2O { A = 4.33E+12 n = .00 E = 18.97 }
1285 B40f: D-C4H6 + CH3 -> S-C4H5 + CH4 { A = 2.63E+01 n = 3.22 E = 47.31 }
1286
1287 # From A-C3H4 + O
1288 B41f: D-C4H6 + O -> C3H6 + CO { A = 9.63E+06 n = 2.05 E = 0.75 }
1289
1290
1291 # 2-Butyne
1292 # --------
1293
1294 B42f: S-C4H6 -> C4H6 { A = 3.00E+13 n = .00 E = 271.96 }
1295 B43f: S-C4H6 -> D-C4H6 { A = 3.00E+13 n = .00 E = 280.33 }
1296 B44f: S-C4H6 + H -> D-C4H6 + H { A = 2.00E+13 n = .00 E = 16.74 }
1297
1298 # Revised using P-C3H4+H->C2H2+CH3
1299 B45f: S-C4H6 + H -> P-C3H4 + CH3 { A = 1.39E+16 n = -0.36 E = 36.11 }
1300
1301 # Peukert, Naumann, Braun-unkhoff 2009
1302 B46f: S-C4H6 -> S-C4H5 + H { A = 3.80E+15 n = .00 E = 373.21 }
1303
1304 # Revised based on C2H6+R
1305 B47f: S-C4H6 + H -> S-C4H5 + H2 { A = 1.70E+05 n = 2.70 E = 24.02 }
1306 B48f: S-C4H6 + O -> S-C4H5 + OH { A = 3.17E+01 n = 3.80 E = 13.10 }
1307 B49f: S-C4H6 + OH -> S-C4H5 + H2O { A = 1.61E+06 n = 2.22 E = 3.10 }
1308 B50f: S-C4H6 + CH3 -> S-C4H5 + CH4 { A = 3.45E+01 n = 3.44 E = 43.47 }
1309
1310 # From C2H2 - Total rate
1311 #B51 : S-C4H6 + O -> C2H3 + CO + CH3 { A = 3.70E+09 n = 1.28 E = 10.34 }
1312 B52 : S-C4H6 + OH -> C2H4 + CO + CH3 { A = 1.86E+03 n = 2.67 E = 0.97 }
1313
1314
1315 # Butadienyl radicals
1316 # -------------------
1317
1318 B53f: C2H3 + C2H2 -> N-C4H5 { A = 9.30E+38 n = -8.76 E = 50.21 }
1319 B54f: C2H3 + C2H2 -> I-C4H5 { A = 1.60E+46 n =-10.98 E = 77.82 }
1320
1321 B55f: C2H3 + C2H3 -> I-C4H5 + H { A = 1.20E+22 n = -2.44 E = 57.13 }
1322 B56f: C2H3 + C2H3 -> N-C4H5 + H { A = 2.40E+20 n = -2.04 E = 64.28 }
1323
1324 B57f: C4H4 + H -> N-C4H5 { A = 1.30E+51 n =-11.92 E = 69.04 }
1325 B58f: C4H4 + H -> I-C4H5 { A = 4.90E+51 n =-11.92 E = 74.06 }
1326
1327 B59f: N-C4H5 -> I-C4H5 { A = 1.50E+67 n =-16.89 E = 247.27 }
1328 B60f: N-C4H5 + H -> I-C4H5 + H { A = 3.10E+26 n = -3.35 E = 72.90 }
1329
1330 B61f: N-C4H5 + H -> C4H4 + H2 { A = 1.50E+13 n = .00 E = .00 }
1331 B62f: N-C4H5 + OH -> C4H4 + H2O { A = 2.50E+12 n = .00 E = .00 }
1332 B63f: N-C4H5 + O2 -> C4H4 + HO2 { A = 6.70E+05 n = 1.61 E = -1.61 }
1333 B64f: N-C4H5 + CH3 -> C4H4 + CH4 { A = 4.52E+12 n = .00 E = -3.20 }
1334
1335 # From C2H3
1336 B66f: N-C4H5 + O -> A-C3H5 + CO { A = 1.03E+13 n = 0.21 E = -1.79 }
1337 B67 : N-C4H5 + O2 -> A-C3H5 + CO + O { A = 3.80E+11 n = 0.19 E = 0.20 }
1338 B68f: N-C4H5 + O2 -> C2H3CHO + HCO { A = 4.05E+17 n = -1.86 E = 4.88 }
1339 B69 : N-C4H5 + O2 -> C2H3CHO + CO + H { A = 2.22E+16 n = -1.35 E = 3.28 }
1340
1341 B70f: I-C4H5 + H -> C3H3 + CH3 { A = 2.00E+13 n = .00 E = 8.37 }
1342
1343 B71f: I-C4H5 + H -> C4H4 + H2 { A = 3.00E+13 n = .00 E = .00 }
1344 B72f: I-C4H5 + OH -> C4H4 + H2O { A = 5.00E+12 n = .00 E = .00 }
1345 B73f: I-C4H5 + O2 -> C4H4 + HO2 { A = 1.34E+06 n = 1.61 E = -1.61 }
1346 B74f: I-C4H5 + CH3 -> C4H4 + CH4 { A = 9.04E+12 n = .00 E = -3.20 }
1347
1348 # From A-C3H5
1349 B75f: I-C4H5 + O -> CH2CO + C2H3 { A = 3.17E+13 n = 0.03 E = -1.65 }
1350 B76 : I-C4H5 + O2 -> CH2CO + C2H2 + OH { A = 9.71E+20 n = -2.70 E = 104.52 }
1351 B77f: I-C4H5 + O2 -> CH2CO + CH2CHO { A = 3.08E+09 n = 0.37 E = 70.75 }
1352 B78 : I-C4H5 + HO2 -> CH2CO + C2H3 + OH { A = 1.19E+09 n = 1.03 E = -9.41 }
1353
1354 B79f: S-C4H5 -> I-C4H5 { A = 1.50E+67 n =-16.89 E = 247.27 }
1355 B80f: S-C4H5 + H -> I-C4H5 + H { A = 3.10E+26 n = -3.35 E = 72.90 }
1356
1357 # From C3H3
1358 #81 : S-C4H5 + O -> C3H2O + CH3 { A = 1.38E+14 n = .00 E = .00 }
1359 B82 : S-C4H5 + O2 -> CH2CO + CH3 + CO { A = 1.70E+05 n = 1.70 E = 6.28 }
1360 B83 : S-C4H5 + HO2 -> C2H2 + CH3 + CO + OH { A = 8.00E+11 n = .00 E = .00 }
1361
1362 # From C3H3+C3H3
1363 B84f: S-C4H5 + C3H3 -> A1CH3-C7H8 { A = 1.87E+46 n = -9.84 E = 70.31 }
1364 B85f: S-C4H5 + C3H3 -> A1CH3*-C7H7 + H { A = 5.77E+37 n = -7.00 E = 131.82 }
1365
1366
1367
1368 #==========================================================================#
1369 # #
1370 # "A Detailed Chemical Kinetic Reaction Mechanism for #
1371 # n-Alkane Hydrocarbons from n-Octane to n-Hexadecane" #
1372 # C. K. Westbrook, W. J. Pitz, O. Herbinet, H. J. Curran and E. J. Silke #
1373 # Combustion and Flame 156:181-199 (2009). #
1374 # #
1375 # LLNL-MI-407455 - version dated 2008-09-02 C.K. Westbrook #
1376 # #
1377 #==========================================================================#
1378
1379
1380 # ------------------- HIGH TEMPERATURE -------------------- #
1381 # ---------------------- 3 Species ------------------------ #
1382 # --------------------- 17 Reactions ---------------------- #
1383
1384 # Reactions of N-C6H14
1385
1386 HX01 : N-C6H14 -> N-C5H11 + CH3 { A = 6.03E+18 n = -0.67 E = 362.13 }
1387 HX02 : N-C6H14 -> N-C4H9 + C2H5 { A = 1.62E+22 n = -1.49 E = 364.80 }
1388 HX03 : N-C6H14 -> N-C3H7 + N-C3H7 { A = 2.62e+22 n = -1.56 E = 367.94 }
1389
1390 HX04 : N-C6H14 + H -> C6H13 + H2 { A = 6.16E+07 n = 2.10 E = 22.91 }
1391 HX05 : N-C6H14 + O -> C6H13 + OH { A = 1.42E+06 n = 2.56 E = 12.62 }
1392 HX06 : N-C6H14 + OH -> C6H13 + H2O { A = 7.49E+06 n = 2.09 E = -2.61 }
1393 HX07 : N-C6H14 + O2 -> C6H13 + HO2 { A = 1.70E+13 n = 0.20 E = 209.99 }
1394 HX08 : N-C6H14 + HO2 -> C6H13 + H2O2 { A = 6.27E+12 n = 0.21 E = 74.05 }
1395
1396 # Reactions of C6H13 (lumped)
1397 # Branching ratios 0.2/0.4
1398
1399 HX09 : C6H13 -> N-C4H9 + C2H4 { A = 3.20E+12 n = 0.13 E = 120.84 }
1400 HX10 : C6H13 -> N-C3H7 + C3H6 { A = 5.52E+12 n = 0.17 E = 125.16 }
1401 HX11 : C6H13 -> C2H5 + C4H8 { A = 2.76E+12 n = 0.17 E = 125.16 }
1402 HX12 : C6H13 -> CH3 + C5H10 { A = 2.76E+12 n = 0.17 E = 125.16 }
1403
1404 HX13 : C6H13 -> C6H12 + H { A = 1.78E+08 n = 1.63 E = 144.24 }
1405
1406 HX14 : C6H13 + HO2 -> C6H13O + OH { A = 7.00E+12 n = .00 E = -4.18 }
1407 HX15 : C6H13 + CH3O2 -> C6H13O + CH3O { A = 7.00E+12 n = .00 E = -4.18 }
1408
1409 # Reactions of C6H13O
1410
1411 HX16 : C6H13O -> N-C5H11 + CH2O { A = 1.19E+18 n = -1.50 E = 84.44 }
1412 HX17 : C6H13O -> N-C4H9 + CH3CHO { A = 7.16E+22 n = -2.78 E = 96.22 }
1413 HX18 : C6H13O -> N-C3H7 + C2H5 + HCO { A = 4.10E+17 n = -1.31 E = 81.60 }
1414
1415
1416
1417 # ------------------- LOW TEMPERATURE -------------------- #
1418 # ---------------------- 5 Species ----------------------- #
1419 # -------------------- 11 Reactions ---------------------- #
1420
1421 /* Commented for now */
1422
1423 # Formation of ROO
1424
1425 HX20 : C6H13 + O2 -> C6H13O2 { A = 1.36E+13 n = -0.08 E = 0.87 }
1426 HX21 : C6H13O2 -> C6H13 + O2 { A = 1.71E+23 n = -2.33 E = 158.32 }
1427 HX22 : C6H13O2 -> C6H12OOH { A = 1.83E+05 n = 1.70 E = 80.90 }
1428
1429 # Reactions of QOOH
1430
1431 HX23 : C6H12OOH -> C6H13O2 { A = 7.53E+04 n = 1.25 E = 24.89 }
1432 HX24 : C6H12OOH -> C6H12 + HO2 { A = 4.01E+00 n = 3.28 E = 53.36 }
1433 HX25 : C6H12OOH -> C6H12O + OH { A = 1.33E+12 n = -0.74 E = 42.56 }
1434 HX26 : C6H12OOH + O2 -> C6H13O4 { A = 7.71E+12 n = -0.01 E = -0.06 }
1435
1436 # Reactions of O2QOOH
1437
1438 HX27 : C6H13O4 -> C6H12OOH + O2 { A = 2.31E+21 n = -1.97 E = 153.05 }
1439 HX28 : C6H13O4 -> OC6H11OOH + OH { A = 6.47E+09 n = 0.18 E = 83.01 }
1440
1441 # Reactions of OQ'OOH
1442 # all products lumped
1443
1444 HX29 : OC6H11OOH -> C2H5 + CH3CHO + CH2CO + OH { A = 3.26E+09 n = 1.93 E = 161.11 }
1445
1446 # Reactions of QO
1447 # all products lumped
1448
1449 HX30: C6H12O + OH -> N-C4H9 + CH2CO + H2O { A = 3.68E+12 n = .00 E = .00 }
1450 /**/
1451
1452
1453 #==========================================================================#
1454 # #
1455 # "A Comprehensive Modeling Study of n-Heptane Oxidation" #
1456 # Curran, H. J., Gaffuri, P., Pitz, W. J., and Westbrook, C. K. #
1457 # Combustion and Flame 114:149-177 (1998). #
1458 # #
1459 # UCRL-WEB-204236 - Review and release date: May 19, 2004. #
1460 # #
1461 #==========================================================================#
1462
1463
1464 # ------------------- HIGH TEMPERATURE -------------------- #
1465 # ---------------------- 3 Species ------------------------ #
1466 # --------------------- 19 Reactions ---------------------- #
1467
1468 # Reactions of N-C7H16
1469
1470 # Rates from LLNL
1471 # Multiplied by 3 to match overall decomp rate from exp
1472 # (Davidson, Oehlschlaeger, Hanson 2007)
1473 HP01 : N-C7H16 -> N-C6H13 + CH3 { A = 8.79E+73 n =-16.61 E = 497.48 }
1474 HP02 : N-C7H16 -> N-C5H11 + C2H5 { A = 2.43E+78 n =-17.62 E = 503.75 }
1475 HP03 : N-C7H16 -> N-C4H9 + N-C3H7 { A = 4.26E+78 n =-17.71 E = 505.01 }
1476
1477 HP04 : N-C7H16 + H -> C7H15 + H2 { A = 9.90E+07 n = 2.06 E = 22.98 }
1478 HP05 : N-C7H16 + O -> C7H15 + OH { A = 1.72E+05 n = 2.81 E = 9.46 }
1479 HP06 : N-C7H16 + OH -> C7H15 + H2O { A = 9.68E+06 n = 2.08 E = -2.73 }
1480 HP07 : N-C7H16 + O2 -> C7H15 + HO2 { A = 2.89E+13 n = 0.20 E = 209.66 }
1481 HP08 : N-C7H16 + HO2 -> C7H15 + H2O2 { A = 7.57E+12 n = 0.21 E = 73.78 }
1482
1483 # Reactions of C7H15 (lumped)
1484 # Branching ratios 0.17/0.33/0.17
1485 # NEW Branching ratios from OH rate about the same at 1000K
1486
1487 HP09 : C7H15 -> N-C5H11 + C2H4 { A = 2.72E+12 n = 0.13 E = 120.84 }
1488 HP10 : C7H15 -> N-C4H9 + C3H6 { A = 4.55E+12 n = 0.17 E = 125.16 }
1489 HP11 : C7H15 -> N-C3H7 + C4H8 { A = 2.28E+12 n = 0.17 E = 125.16 }
1490 HP12 : C7H15 -> C2H5 + C5H10 { A = 2.35E+12 n = 0.17 E = 125.16 }
1491 HP13 : C7H15 -> CH3 + C6H12 { A = 2.28E+12 n = 0.17 E = 125.16 }
1492
1493 HP14 : C7H15 -> C7H14 + H { A = 1.78E+08 n = 1.63 E = 144.24 }
1494
1495 HP15 : C7H15 + HO2 -> C7H15O + OH { A = 7.00E+12 n = .00 E = -4.18 }
1496 HP16 : C7H15 + CH3O2 -> C7H15O + CH3O { A = 7.00E+12 n = .00 E = -4.18 }
1497
1498 # Reactions of C7H15O (lumped)
1499
1500 HP17 : C7H15O -> N-C5H11 + CH3CHO { A = 8.92E+19 n = -2.03 E = 87.88 }
1501 HP18 : C7H15O -> N-C4H9 + C2H5 + HCO { A = 2.23E+15 n = -0.70 E = 77.85 }
1502 HP19 : C7H15O -> N-C3H7 + N-C3H7 + HCO { A = 6.18E+16 n = -1.36 E = 77.48 }
1503
1504
1505 # ------------------- LOW TEMPERATURE -------------------- #
1506 # ---------------------- 5 Species ----------------------- #
1507 # -------------------- 11 Reactions ---------------------- #
1508
1509 /* Commented for now */
1510
1511 # Formation of ROO
1512
1513 HP20: C7H15 + O2 -> C7H15O2 { A = 1.68E+13 n = -0.11 E = 1.01 }
1514 HP21: C7H15O2 -> C7H15 + O2 { A = 1.92E+22 n = -2.11 E = 156.08 }
1515 HP22: C7H15O2 -> C7H14OOH { A = 1.88E+05 n = 1.68 E = 79.51 }
1516
1517 # Reactions of QOOH
1518
1519 HP23: C7H14OOH -> C7H15O2 { A = 7.64E+05 n = 0.91 E = 25.45 }
1520 HP24: C7H14OOH -> C7H14 + HO2 { A = 5.85E+03 n = 2.40 E = 64.08 }
1521 HP25: C7H14OOH -> C7H14O + OH { A = 3.97E-10 n = 5.69 E = 1.57 }
1522 HP26: C7H14OOH + O2 -> C7H15O4 { A = 1.51E+13 n = -0.09 E = 0.53 }
1523
1524 # Reactions of O2QOOH
1525
1526 HP27: C7H15O4 -> C7H14OOH + O2 { A = 1.71E+22 n = -2.13 E = 155.32 }
1527 HP28: C7H15O4 -> OC7H13OOH + OH { A = 4.25E+10 n = -0.11 E = 81.48 }
1528
1529 # Reactions of OQ'OOH
1530 # all products lumped
1531
1532 HP29: OC7H13OOH -> N-C3H7 + CH3CHO + CH2CO + OH { A = 3.26E+09 n = 1.93 E = 161.11 }
1533
1534 # Reactions of QO
1535 # all products lumped
1536
1537 HP30: C7H14O + OH -> N-C5H11 + CH2CO + H2O { A = 3.68E+12 n = .00 E = .00 }
1538 /**/
1539
1540
1541
1542 #==========================================================================#
1543 # #
1544 # "A Detailed Chemical Kinetic Reaction Mechanism for #
1545 # n-Alkane Hydrocarbons from n-Octane to n-Hexadecane" #
1546 # C. K. Westbrook, W. J. Pitz, O. Herbinet, H. J. Curran and E. J. Silke #
1547 # Combustion and Flame 156:181-199 (2009). #
1548 # #
1549 # LLNL-MI-407455 - version dated 2008-09-02 C.K. Westbrook #
1550 # #
1551 #==========================================================================#
1552
1553
1554 # H-abs by H from Cartensen & Dean 2009
1555 # H-abs by OH from Kwok & Atkinson 1995 / Pang, Hanson et al. 2011
1556 # Total decomp rate fitted to McDonald 2012 and Klingbeil et al. 2008
1557 # -> individual rates rescaled with same branching ratios
1558
1559 # ------------------- HIGH TEMPERATURE -------------------- #
1560 # ---------------------- 3 Species ------------------------ #
1561 # --------------------- 73 Reactions ---------------------- #
1562
1563 # Reactions of N-C12H26
1564
1565 DD01 : N-C12H26 -> N-C10H21 + C2H5 { A = 1.68E+24 n = -2.11 E = 368.84 }
1566 DD02 : N-C12H26 -> N-C9H19 + N-C3H7 { A = 2.46E+24 n = -2.12 E = 371.27 }
1567 DD03 : N-C12H26 -> N-C8H17 + N-C4H9 { A = 1.21E+24 n = -2.07 E = 369.64 }
1568 DD04 : N-C12H26 -> N-C7H15 + N-C5H11 { A = 1.13E+24 n = -2.06 E = 369.58 }
1569 DD05 : N-C12H26 -> N-C6H13 + N-C6H13 { A = 2.59E+24 n = -2.12 E = 369.69 }
1570
1571 DD06 : N-C12H26 + H -> C12H25 + H2 { A = 3.59E+08 n = 1.97 E = 23.16 }
1572 DD07 : N-C12H26 + O -> C12H25 + OH { A = 3.97E+05 n = 2.76 E = 9.19 }
1573 DD08 : N-C12H26 + OH -> C12H25 + H2O { A = 2.18E+07 n = 2.05 E = -2.95 }
1574 DD09 : N-C12H26 + O2 -> C12H25 + HO2 { A = 1.05E+14 n = 0.10 E = 209.77 }
1575 DD10 : N-C12H26 + HO2 -> C12H25 + H2O2 { A = 2.86E+13 n = 0.11 E = 73.93 }
1576
1577 # Reactions of C12H25 (lumped)
1578 # Branching ratios 0.09/.18
1579 # NEW Branching ratios from OH rate about same at 1000K
1580
1581 DD11 : C12H25 -> N-C10H21 + C2H4 { A = 1.44E+12 n = 0.13 E = 120.84 }
1582 DD12 : C12H25 -> N-C9H19 + C3H6 { A = 2.48E+12 n = 0.17 E = 125.16 }
1583 DD13 : C12H25 -> N-C8H17 + C4H8 { A = 2.48E+12 n = 0.17 E = 125.16 }
1584 DD14 : C12H25 -> N-C7H15 + C5H10 { A = 1.24E+12 n = 0.17 E = 125.16 }
1585 DD15 : C12H25 -> N-C6H13 + C6H12 { A = 1.24E+12 n = 0.17 E = 125.16 }
1586 DD16 : C12H25 -> N-C5H11 + C7H14 { A = 1.24E+13 n = 0.17 E = 125.16 }
1587 DD17 : C12H25 -> N-C4H9 + C8H16 { A = 1.24E+13 n = 0.17 E = 125.16 }
1588 DD18 : C12H25 -> N-C3H7 + C9H18 { A = 1.24E+12 n = 0.17 E = 125.16 }
1589 DD19 : C12H25 -> C2H5 + C10H20 { A = 1.24E+12 n = 0.17 E = 125.16 }
1590
1591 DD20 : C12H25 -> C12H24 + H { A = 1.78E+08 n = 1.63 E = 144.24 }
1592
1593 DD21 : C12H25 + HO2 -> C12H25O + OH { A = 7.00E+12 n = .00 E = -4.18 }
1594 DD22 : C12H25 + CH3O2 -> C12H25O + CH3O { A = 7.00E+12 n = .00 E = -4.18 }
1595
1596 # Reactions of C12H25O
1597
1598 DD23 : C12H25O -> N-C10H21 + CH3CHO { A = 4.35E+08 n = 1.31 E = 64.79 }
1599 DD24 : C12H25O -> N-C9H19 + C2H5 + HCO { A = 8.37E+18 n = -1.84 E = 82.98 }
1600 DD25 : C12H25O -> N-C8H17 + N-C3H7 + HCO { A = 9.83E+44 n = -9.70 E = 134.38 }
1601 DD26 : C12H25O -> N-C7H15 + N-C4H9 + HCO { A = 8.35E+61 n =-14.50 E = 179.77 }
1602 DD27 : C12H25O -> N-C6H13 + N-C5H11 + HCO { A = 4.63E+64 n =-15.38 E = 182.82 }
1603
1604 # Reactions of C12H24 (lumped)
1605
1606 DD28 : C12H24 -> N-C9H19 + A-C3H5 { A = 9.53E+15 n = -0.18 E = 298.01 }
1607 DD32 : C12H24 -> N-C8H17 + C4H7 { A = 1.87E+15 n = 0.04 E = 296.85 }
1608 DD31 : C12H24 -> N-C7H15 + C5H9 { A = 1.50E+15 n = -0.02 E = 297.10 }
1609 DD30 : C12H24 -> N-C5H11 + C7H13 { A = 2.08E+15 n = -0.04 E = 297.23 }
1610 DD29 : C12H24 -> N-C4H9 + C8H15 { A = 1.51E+13 n = 0.52 E = 294.52 }
1611
1612 DD33 : C12H24 + H -> C12H23 + H2 { A = 3.70E+13 n = .00 E = 16.32 }
1613 DD34 : C12H24 + OH -> C12H23 + H2O { A = 3.00E+13 n = .00 E = 5.15 }
1614
1615 # Reactions of C12H23 (lumped)
1616
1617 DD35 : C12H23 -> C10H19 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1618 DD36 : C12H23 -> C9H17 + C3H6 { A = 1.38E+13 n = 0.17 E = 125.16 }
1619 DD37 : C12H23 -> C8H15 + C4H8 { A = 1.38E+13 n = 0.17 E = 125.16 }
1620 DD38 : C12H23 -> C7H13 + C5H10 { A = 1.38E+13 n = 0.17 E = 125.16 }
1621 DD39 : C12H23 -> C5H9 + C7H14 { A = 1.38E+13 n = 0.17 E = 125.16 }
1622 DD40 : C12H23 -> C4H7 + C8H16 { A = 1.38E+13 n = 0.17 E = 125.16 }
1623 DD41 : C12H23 -> A-C3H5 + C9H18 { A = 1.38E+13 n = 0.17 E = 125.16 }
1624 DD42 : C12H23 -> C2H3 + C10H20 { A = 1.38E+13 n = 0.17 E = 125.16 }
1625
1626
1627
1628
1629 # -------------------- LOW TEMPERATURE -------------------- #
1630 # ----------------------- 10 Species ---------------------- #
1631 # ---------------------- 21 Reactions --------------------- #
1632 /**/
1633 # Reactions of C12H25O2
1634 # Backward rate reduced (x1/6)
1635 # to mimic lumping of peroxy species
1636
1637 DD50 : C12H25 + O2 -> C12H25O2 { A = 9.52E+12 n = -0.04 E = 0.23 }
1638 DD51 : C12H25O2 -> C12H25 + O2 { A = 1.52E+22 n = -2.31 E = 156.59 }
1639 DD52 : C12H25O2 -> C12H24OOH { A = 1.13E+06 n = 1.46 E = 80.17 }
1640 DD53 : C12H24OOH -> C12H25O2 { A = 4.47E+21 n = -3.86 E = 58.11 }
1641
1642 # Reactions of C12H24OOH
1643
1644 DD54 : C12H24OOH -> C12H24 + HO2 { A = 2.21E+14 n = -0.81 E = 84.74 }
1645 DD55 : C12H24OOH -> C12H24O + OH { A = 3.25E-11 n = 5.92 E = -7.84 }
1646 DD56 : C12H24OOH + O2 -> C12H25O4 { A = 1.32E+13 n = -0.08 E = 0.47 }
1647
1648 # Reactions of C12H25O4
1649
1650 DD57 : C12H25O4 -> C12H24OOH + O2 { A = 1.92E+23 n = -2.42 E = 157.60 }
1651 DD58 : C12H25O4 -> C12H24O3 + OH { A = 1.28E+07 n = 0.89 E = 72.18 }
1652
1653 # Reactions of C12H24O3
1654 # lump all decomposition pathways
1655
1656 DD59 : C12H24O3 -> N-C8H17 + CH3CHO + CH2CO + OH{ A = 8.95E+14 n = 0.32 E = 171.10 }
1657
1658 # Reactions of C12H24O
1659 # lump all decomposition pathways
1660
1661 DD60 : C12H24O + OH -> N-C8H17 + C2H4 + CH2CO + H2O{ A = 3.09E+13 n = -0.27 E = 1.61 }
1662
1663 # Reactions of C8H17O2
1664
1665 DD61 : N-C8H17 + O2 -> C8H17O2 { A = 1.65E+22 n = -2.85 E = 19.78 }
1666 DD62 : C8H17O2 -> N-C8H17 + O2 { A = 2.48E+21 n = -1.94 E = 150.73 }
1667 DD63 : C8H17O2 -> C8H16OOH { A = 1.11E+06 n = 1.40 E = 79.77 }
1668
1669 # Reactions of C8H16OOH
1670
1671 DD64 : C8H16OOH -> C8H16O + OH { A = 3.07E+02 n = 2.15 E = 24.57 }
1672 DD65 : C8H16OOH -> C8H16 + HO2 { A = 5.11E+06 n = 1.40 E = 70.08 }
1673 DD66 : C8H16OOH + O2 -> C8H17O4 { A = 1.16E+11 n = 0.53 E = -3.58 }
1674
1675 # Reactions of C8H17O4/C8H16O3
1676
1677 DD67 : C8H17O4 -> C8H16OOH + O2 { A = 1.37E+23 n = -2.37 E = 157.49 }
1678 DD68 : C8H17O4 -> C8H16O3 + OH { A = 9.98E+06 n = 1.02 E = 83.92 }
1679 DD69 : C8H16O3 -> N-C4H9 + CH3CHO + CH2CO + OH { A = 4.44E+32 n = -4.98 E = 207.98 }
1680
1681 DD70 : C8H16O + OH -> N-C6H13 + CH2CO + H2O { A = 3.09E+13 n = -0.27 E = 1.61 }
1682 /**/
1683
1684
1685
1686 #==========================================================================#
1687 # #
1688 # Additional n-alkyl mechanism #
1689 # (based on) #
1690 # Lawrence Livermore n-Alkanes Mechanism - ver 2 #
1691 # #
1692 #==========================================================================#
1693
1694
1695 # ------------------- HIGH TEMPERATURE -------------------- #
1696 # ---------------------- 21 Species ----------------------- #
1697 # --------------------- 70 Reactions ---------------------- #
1698
1699 # H-abstractions from Miller & Klippenstein 2013 - HPL
1700 # p -> { A = 1.78E+08 n = 1.63 E = 144.24 }
1701 # Beta scissions from Ratkiewicz & Truong 2012 - HPL
1702 # p -> { A = 1.60E+13 n = 0.13 E = 120.84 }
1703 # st -> { A = 1.38E+13 n = 0.17 E = 125.16 }
1704 # H-abstraction for alkane from Cartensen & Dean 2009
1705 # p -> { A = 1.40E+07 n = 1.97 E = 34.31 }
1706 # s -> { A = 3.80E+07 n = 1.86 E = 23.43 }
1707 # N-alkene decomposition from Manion & Awan 2015
1708 # { A = 3.39E+15 n = .00 E = 302.40 }
1709
1710
1711 # Decyl radical
1712 # -------------
1713
1714 # Reactions of N-C10H21
1715
1716 NC01 : N-C10H21 -> N-C8H17 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1717 NC02 : N-C10H21 -> C10H20 + H { A = 2.04E+10 n = 0.95 E = 141.45 }
1718
1719 # Reactions of C10H20
1720
1721 NC03 : C10H20 -> N-C7H15 + A-C3H5 { A = 3.39E+15 n = .00 E = 302.40 }
1722
1723 NC04 : C10H20 + H -> C10H19 + H2 { A = 3.70E+13 n = .00 E = 16.32 }
1724 NC05 : C10H20 + OH -> C10H19 + H2O { A = 3.00E+13 n = .00 E = 5.15 }
1725
1726 # Reactions of C10H19 (lumped)
1727
1728 NC06 : C10H19 -> C8H15 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1729 NC07 : C10H19 -> C7H13 + C3H6 { A = 1.38E+13 n = 0.17 E = 125.16 }
1730 NC08 : C10H19 -> C6H11 + C4H8 { A = 1.38E+13 n = 0.17 E = 125.16 }
1731 NC09 : C10H19 -> C5H9 + C5H10 { A = 1.38E+13 n = 0.17 E = 125.16 }
1732 NC10 : C10H19 -> C4H7 + C6H12 { A = 1.38E+13 n = 0.17 E = 125.16 }
1733 NC11 : C10H19 -> A-C3H5 + C7H14 { A = 1.38E+13 n = 0.17 E = 125.16 }
1734 NC12 : C10H19 -> C2H3 + C8H16 { A = 1.38E+13 n = 0.17 E = 125.16 }
1735
1736
1737 # Nonyl radical
1738 # -------------
1739
1740 # Reactions of N-C9H19
1741
1742 NC13 : N-C9H19 -> N-C7H15 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1743 NC14 : N-C9H19 -> C9H18 + H { A = 2.04E+10 n = 0.95 E = 141.45 }
1744
1745 # Reactions of C9H18
1746
1747 NC15 : C9H18 -> N-C6H13 + A-C3H5 { A = 3.39E+15 n = .00 E = 302.40 }
1748
1749 NC16 : C9H18 + H -> C9H17 + H2 { A = 3.70E+13 n = .00 E = 16.32 }
1750 NC17 : C9H18 + OH -> C9H17 + H2O { A = 3.00E+13 n = .00 E = 5.15 }
1751
1752 # Reactions of C9H17 (lumped)
1753
1754 NC18 : C9H17 -> C7H13 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1755 NC19 : C9H17 -> C6H11 + C3H6 { A = 1.38E+13 n = 0.17 E = 125.16 }
1756 NC20 : C9H17 -> C5H9 + C4H8 { A = 1.38E+13 n = 0.17 E = 125.16 }
1757 NC21 : C9H17 -> C4H7 + C5H10 { A = 1.38E+13 n = 0.17 E = 125.16 }
1758 NC22 : C9H17 -> A-C3H5 + C6H12 { A = 1.38E+13 n = 0.17 E = 125.16 }
1759 NC23 : C9H17 -> C2H3 + C7H14 { A = 1.38E+13 n = 0.17 E = 125.16 }
1760
1761
1762 # Octyl radical
1763 # -------------
1764
1765 # Reactions of N-C8H17
1766
1767 NC24 : N-C8H17 -> N-C6H13 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1768 NC25 : N-C8H17 -> C8H16 + H { A = 2.04E+10 n = 0.95 E = 141.45 }
1769
1770 # Reactions of C8H16
1771
1772 NC26 : C8H16 -> N-C5H11 + A-C3H5 { A = 3.39E+15 n = .00 E = 302.40 }
1773
1774 NC27 : C8H16 + H -> C8H15 + H2 { A = 3.70E+13 n = .00 E = 16.32 }
1775 NC28 : C8H16 + OH -> C8H15 + H2O { A = 3.00E+13 n = .00 E = 5.15 }
1776
1777 # Reactions of C8H15 (lumped)
1778
1779 NC29 : C8H15 -> C6H11 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1780 NC30 : C8H15 -> C5H9 + C3H6 { A = 1.38E+13 n = 0.17 E = 125.16 }
1781 NC31 : C8H15 -> C4H7 + C4H8 { A = 1.38E+13 n = 0.17 E = 125.16 }
1782 NC32 : C8H15 -> A-C3H5 + C5H10 { A = 1.38E+13 n = 0.17 E = 125.16 }
1783 NC33 : C8H15 -> C2H3 + C6H12 { A = 1.38E+13 n = 0.17 E = 125.16 }
1784
1785
1786 # Heptyl radical
1787 # --------------
1788
1789 # Reactions of N-C7H15
1790
1791 NC34 : N-C7H15 -> N-C5H11 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1792 NC35 : N-C7H15 -> C7H14 + H { A = 2.04E+10 n = 0.95 E = 141.45 }
1793
1794 # Reactions of C7H14
1795
1796 NC36 : C7H14 -> N-C4H9 + A-C3H5 { A = 3.39E+15 n = .00 E = 302.40 }
1797
1798 NC37 : C7H14 + H -> C7H13 + H2 { A = 3.70E+13 n = .00 E = 16.32 }
1799 NC38 : C7H14 + OH -> C7H13 + H2O { A = 3.00E+13 n = .00 E = 5.15 }
1800
1801 # Reactions of C7H13 (lumped)
1802
1803 NC39 : C7H13 -> C5H9 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1804 NC40 : C7H13 -> C4H7 + C3H6 { A = 1.38E+13 n = 0.17 E = 125.16 }
1805 NC41 : C7H13 -> A-C3H5 + C4H8 { A = 1.38E+13 n = 0.17 E = 125.16 }
1806 NC42 : C7H13 -> C2H3 + C5H10 { A = 1.38E+13 n = 0.17 E = 125.16 }
1807
1808
1809 # Hexyl radical
1810 # -------------
1811
1812 # Reactions of N-C6H13
1813
1814 NC43 : N-C6H13 -> N-C4H9 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1815 NC44 : N-C6H13 -> C6H12 + H { A = 2.04E+10 n = 0.95 E = 141.45 }
1816
1817 # Reactions of C6H12
1818
1819 NC45 : C6H12 -> N-C3H7 + A-C3H5 { A = 8.52E+26 n = -3.39 E = 320.10 }
1820
1821 NC46 : C6H12 + H -> C6H11 + H2 { A = 3.70E+13 n = .00 E = 16.32 }
1822 NC47 : C6H12 + OH -> C6H11 + H2O { A = 3.00E+13 n = .00 E = 5.15 }
1823
1824 # Reactions of C6H11 (lumped)
1825
1826 NC48 : C6H11 -> C4H7 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1827 NC49 : C6H11 -> A-C3H5 + C3H6 { A = 1.38E+13 n = 0.17 E = 125.16 }
1828 NC50 : C6H11 -> C2H3 + C4H8 { A = 1.38E+13 n = 0.17 E = 125.16 }
1829
1830
1831 # Pentyl radical
1832 # --------------
1833
1834 # Reactions of N-C5H11
1835
1836 NC51 : N-C5H11 -> N-C3H7 + C2H4 { A = 3.24E+12 n = 0.32 E = 120.53 }
1837 NC52 : N-C5H11 -> C3H6 + C2H5 { A = 1.15E+01 n = 3.03 E = 64.07 }
1838 NC53 : N-C5H11 -> C5H10 + H { A = 2.04E+10 n = 0.95 E = 141.45 }
1839
1840 # Reactions of C5H10
1841
1842 NC54 : C5H10 -> A-C3H5 + C2H5 { A = 3.39E+15 n = .00 E = 302.40 }
1843
1844 NC55 : C5H10 + H -> C5H9 + H2 { A = 3.70E+13 n = .00 E = 16.32 }
1845 NC56 : C5H10 + OH -> C5H9 + H2O { A = 3.00E+13 n = .00 E = 5.15 }
1846
1847 # Reactions of C5H9 (lumped)
1848
1849 NC57 : C5H9 -> A-C3H5 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1850 NC58 : C5H9 -> C2H3 + C3H6 { A = 1.38E+13 n = 0.17 E = 125.16 }
1851
1852
1853 # Butyl radical
1854 # -------------
1855
1856 # Reactions of N-C4H9
1857
1858 NC59 : N-C4H9 -> C2H5 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1859 NC60 : N-C4H9 -> C4H8 + H { A = 2.04E+10 n = 0.95 E = 141.45 }
1860
1861 # Reactions of C4H8 reactions
1862
1863 # Manion, Awan 2015
1864 NC61 : C4H8 -> A-C3H5 + CH3 { A = 3.39E+15 n = .00 E = 302.40 }
1865 NC62 : C4H8 + H -> C3H6 + CH3 { A = 1.05E+09 n = 1.40 E = 3.04 }
1866 NC63 : C4H8 + H -> C2H5 + C2H4 { A = 9.02E+08 n = 1.40 E = 9.66 }
1867
1868 NC64 : C4H8 + H -> C4H7 + H2 { A = 3.70E+13 n = .00 E = 16.32 }
1869 NC65 : C4H8 + OH -> C4H7 + H2O { A = 3.00E+13 n = .00 E = 5.15 }
1870
1871 # Reactions of C4H7
1872
1873 NC66 : C4H7 -> C2H4 + C2H3 { A = 1.00E+11 n = .00 E = 154.81 }
1874 NC67 : C4H7 -> C4H6 + H { A = 1.20E+14 n = .00 E = 206.27 }
1875
1876 NC68 : C4H7 + H -> C4H6 + H2 { A = 3.16E+13 n = .00 E = .00 }
1877 NC69 : C4H7 + O2 -> C4H6 + HO2 { A = 1.00E+09 n = .00 E = .00 }
1878 NC70 : C4H7 + CH3 -> C4H6 + CH4 { A = 8.00E+12 n = .00 E = .00 }
1879
1880 NC71 : C4H7 + HO2 -> A-C3H5 + CH2O + OH { A = 7.00E+12 n = .00 E = -4.18 }
1881 NC72 : C4H7 + CH3O2 -> A-C3H5 + CH2O + CH3O { A = 7.00E+12 n = .00 E = -4.18 }
1882
1883
1884
1885
1886 #==========================================================================#
1887 # #
1888 # M. Mehl, H. J. Curran, W. J. Pitz, and C. K. Westbrook, 2009 #
1889 # LLNL-MI-421507 - Review and release date: December 16, 2009 #
1890 # #
1891 #==========================================================================#
1892
1893
1894 # ------------------- HIGH TEMPERATURE -------------------- #
1895 # ---------------------- 15 Species ----------------------- #
1896 # --------------------- 73 Reactions ---------------------- #
1897
1898 # Reactions of I-C8H18
1899
1900 IC00 : I-C8H18 -> Y-C7H15 + CH3 { A = 6.18E+25 n = -2.46 E = 350.24 }
1901 IC01 : I-C8H18 -> T-C4H8 + I-C3H7 + CH3 { A = 2.46E+23 n = -2.01 E = 348.95 }
1902 IC02 : I-C8H18 -> 2 T-C4H9 { A = 7.83E+29 n = -3.93 E = 352.08 }
1903
1904 IC03 : I-C8H18 + H -> C-C8H17 + H2 { A = 9.08E+00 n = 4.12 E = 7.45 }
1905 IC04 : I-C8H18 + O -> C-C8H17 + OH { A = 4.69E+03 n = 3.19 E = 4.52 }
1906 IC05 : I-C8H18 + OH -> C-C8H17 + H2O { A = 2.70E+05 n = 2.43 E = -4.04 }
1907 IC06 : I-C8H18 + O2 -> C-C8H17 + HO2 { A = 1.03E+11 n = 0.84 E = 196.29 }
1908 IC07 : I-C8H18 + CH3 -> C-C8H17 + CH4 { A = 1.14E-18 n = 9.25 E = -8.89 }
1909 IC08 : I-C8H18 + HO2 -> C-C8H17 + H2O2 { A = 9.85E+10 n = 0.73 E = 70.89 }
1910 IC09 : I-C8H18 + CH3O2 -> C-C8H17 + CH3O + OH { A = 9.85E+10 n = 0.73 E = 70.89 }
1911
1912 # Reactions of C-C8H17
1913
1914 IC10 : C-C8H17 -> Y-C7H14 + CH3 { A = 2.55E+39 n = -7.47 E = 189.48 }
1915 IC11 : C-C8H17 -> T-C4H9 + T-C4H8 { A = 4.28E+22 n = -2.81 E = 127.70 }
1916 IC12 : C-C8H17 -> T-C4H8 + CH3 + C3H6 { A = 4.22E+24 n = -3.34 E = 158.66 }
1917
1918 IC13 : C-C8H17 + HO2 -> D-C8H17O + OH { A = 7.00E+12 n = .00 E = -4.18 }
1919 IC14 : C-C8H17 + CH3O2 -> D-C8H17O + CH3O { A = 7.00E+12 n = .00 E = -4.18 }
1920
1921 # Reactions of D-C8H17O
1922
1923 IC15 : D-C8H17O -> T-C4H8 + CH3 + CH3COCH3 { A = 1.33E+23 n = -2.98 E = 64.44 }
1924 IC16 : D-C8H17O -> T-C4H9 + I-C3H7 + HCO { A = 7.95E+33 n = -6.00 E = 97.57 }
1925 IC17 : D-C8H17O -> Y-C7H15 + CH2O { A = 2.69E+20 n = -2.08 E = 62.99 }
1926
1927 # Reactions of Y-C7H15
1928
1929 IC18 : Y-C7H15 -> T-C4H9 + C3H6 { A = 5.14E+23 n = -2.93 E = 131.78 }
1930 IC19 : Y-C7H15 -> T-C4H8 + I-C3H7 { A = 5.87E+21 n = -2.57 E = 136.80 }
1931 IC20 : Y-C7H15 -> Y-C7H14 + H { A = 6.13E+13 n = 0.03 E = 153.44 }
1932
1933 # Reactions of Y-C7H14
1934
1935 IC21 : Y-C7H14 -> T-C4H9 + A-C3H5 { A = 3.98E+26 n = -3.48 E = 320.14 }
1936 IC22 : Y-C7H14 -> T-C4H7 + I-C3H7 { A = 5.29E+24 n = -2.55 E = 317.38 }
1937
1938 IC23 : Y-C7H14 + H -> X-C7H13 + H2 { A = 2.38E-13 n = 7.67 E = -47.65 }
1939 IC24 : Y-C7H14 + OH -> X-C7H13 + H2O { A = 6.46E-09 n = 6.18 E = -41.33 }
1940
1941 # Reactions of X-C7H13
1942
1943 IC25 : X-C7H13 -> T-C4H9 + A-C3H4 { A = 8.71E+21 n = -2.43 E = 249.07 }
1944 IC26 : X-C7H13 -> T-C4H8 + T-C3H5 { A = 6.32E+18 n = -1.80 E = 182.42 }
1945 IC27 : X-C7H13 -> T-C4H7 + C3H6 { A = 2.10E+16 n = -1.09 E = 74.56 }
1946
1947 #C28 : X-C7H13 + HO2 -> I-C3H5CHO + I-C3H7 + OH { A = 1.00E+13 n = .00 E = .00 }
1948
1949 # Reactions of T-C4H9
1950
1951 # Ratkeiwicz 2011 (x0.5 for lumping)
1952 IC29 : T-C4H9 -> C3H6 + CH3 { A = 3.30E+12 n = 0.37 E = 128.58 }
1953
1954 IC30 : T-C4H9 -> T-C4H8 + H { A = 5.35E+10 n = 1.06 E = 137.99 }
1955
1956 #C31 : T-C4H9 + HO2 -> T-C4H9O + OH { A = 7.00E+12 n = .00 E = -4.18 }
1957 #C32 : T-C4H9 + CH3O2 -> T-C4H9O + CH3O { A = 7.00E+12 n = .00 E = -4.18 }
1958
1959 # Reactions of T-C4H9O
1960
1961 #C33 : T-C4H9O -> I-C3H7 + HCO + H { A = 1.78E+39 n = -7.30 E = 156.05 }
1962 #C34 : T-C4H9O -> I-C3H7 + CH2O { A = 7.25E+39 n = -7.59 E = 140.03 }
1963 #C35 : T-C4H9O -> CH3COCH3 + CH3 { A = 3.09E+13 n = 0.03 E = 58.87 }
1964
1965 # Reactions of T-C4H8
1966 # (not lumped)
1967
1968 IC36 : T-C4H8 -> T-C3H5 + CH3 { A = 1.92E+66 n =-14.22 E = 535.97 }
1969 IC37 : T-C4H8 + H -> C3H6 + CH3 { A = 5.68E+33 n = -5.72 E = 83.68 }
1970
1971 IC38 : T-C4H8 + H -> T-C4H7 + H2 { A = 3.40E+05 n = 2.50 E = 10.43 }
1972 IC39 : T-C4H8 + O -> T-C4H7 + OH { A = 1.21E+11 n = 0.70 E = 31.94 }
1973 IC40 : T-C4H8 + OH -> T-C4H7 + H2O { A = 5.20E+06 n = 2.00 E = -1.25 }
1974 IC41 : T-C4H8 + CH3 -> T-C4H7 + CH4 { A = 4.42E+00 n = 3.50 E = 23.74 }
1975 IC42 : T-C4H8 + HO2 -> T-C4H7 + H2O2 { A = 1.93E+04 n = 2.60 E = 58.20 }
1976
1977 #C43 : T-C4H8 + O -> I-C3H7 + HCO { A = 1.58E+07 n = 1.76 E = -5.09 }
1978 #C44 : T-C4H8 + O -> CH2CO + 2 CH3 { A = 3.33E+07 n = 1.76 E = 0.32 }
1979
1980 # Reactions of T-C4H7
1981 # (not lumped)
1982
1983 IC45 : T-C4H7 -> A-C3H4 + CH3 { A = 1.23E+47 n = -9.74 E = 310.70 }
1984
1985 #C46 : T-C4H7 + O -> I-C3H5CHO + H { A = 6.03E+13 n = .00 E = .00 }
1986 #C47 : T-C4H7 + O2 -> I-C3H5CHO + OH { A = 2.47E+13 n = -0.45 E = 96.32 }
1987 #C48 : T-C4H7 + O2 -> CH2CO + CH2O + CH3 { A = 7.14E+15 n = -1.21 E = 88.07 }
1988 #C49 : T-C4H7 + O2 -> A-C3H4 + CH2O + OH { A = 7.29E+29 n = -5.71 E = 89.75 }
1989 #C50 : T-C4H7 + HO2 -> T-C4H7O + OH { A = 7.00E+12 n = .00 E = -4.18 }
1990
1991 # Reactions of T-C4H7O
1992 # (not lumped)
1993
1994 #C51 : T-C4H7O -> I-C3H5CHO + H { A = 5.00E+13 n = .00 E = 121.75 }
1995 #C52 : T-C4H7O -> T-C3H5 + CH2O { A = 2.93E+21 n = -2.39 E = 148.91 }
1996 #C53 : T-C4H7O + O2 -> I-C3H5CHO + HO2 { A = 3.00E+10 n = .00 E = 6.90 }
1997
1998 # Reactions of I-C3H5CHO
1999 # (not lumped)
2000
2001 #C54 : I-C3H5CHO -> T-C3H5 + HCO { A = 3.05E+23 n = -2.37 E = 415.22 }
2002
2003 #C55 : I-C3H5CHO + H -> T-C3H5 + CO + H2 { A = 2.60E+12 n = .00 E = 10.88 }
2004 #C56 : I-C3H5CHO + O -> T-C3H5 + CO + OH { A = 7.18E+12 n = .00 E = 5.81 }
2005 #C57 : I-C3H5CHO + OH -> T-C3H5 + CO + H2O { A = 2.69E+10 n = 0.76 E = -1.42 }
2006 #C58 : I-C3H5CHO + CH3 -> T-C3H5 + CO + CH4 { A = 3.98E+12 n = .00 E = 36.40 }
2007 #C59 : I-C3H5CHO + HO2 -> T-C3H5 + CO + H2O2 { A = 1.00E+12 n = .00 E = 49.87 }
2008
2009 # Reactions of CH3COCH3
2010 # Revised from LLNL-NC16
2011 # (not lumped)
2012
2013 IC60 : CH3COCH3 -> 2 CH3 + CO { A = 1.22E+23 n = -1.99 E = 351.25 }
2014
2015 IC61 : CH3COCH3 + H -> CH2CO + CH3 + H2 { A = 2.30E+05 n = 2.72 E = 26.19 }
2016 IC62 : CH3COCH3 + O -> CH2CO + CH3 + OH { A = 5.13E+11 n = 0.21 E = 20.46 }
2017 IC63 : CH3COCH3 + OH -> CH2CO + CH3 + H2O { A = 3.38E+07 n = 1.74 E = 3.47 }
2018 IC64 : CH3COCH3 + O2 -> CH2CO + CH3 + HO2 { A = 6.03E+13 n = .00 E = 202.92 }
2019 IC65 : CH3COCH3 + CH3 -> CH2CO + CH3 + CH4 { A = 3.96E+11 n = .00 E = 40.94 }
2020 IC66 : CH3COCH3 + HO2 -> CH2CO + CH3 + H2O2 { A = 1.70E+13 n = .00 E = 85.61 }
2021
2022
2023
2024 #==========================================================================#
2025 # #
2026 # Zhong & Bozzelli, Int. J. Chem. Kinet., 1997, 29, 893-913 #
2027 # Zhong & Bozzelli, J. Phys. Chem. A, 1998, 102, 3537-3555 #
2028 # Robinson & Lindstedt, Comb. Flame, 2011, 158, 666-686 #
2029 # #
2030 #==========================================================================#
2031
2032
2033 # Cyclopentadiene
2034 # ---------------
2035
2036 # Robinson & Lindstedt 2011
2037 CP01f: C5H6 -> C5H5 + H { A = 3.24E+49 n =-10.01 E = 423.40 }
2038 CP02f: C5H6 + H -> C5H5 + H2 { A = 8.59E+07 n = 1.85 E = 13.97 }
2039
2040 CP03f: C5H6 + H -> A-C3H5 + C2H2 { A = 7.74E+36 n = -6.81 E = 137.60 }
2041
2042 CP04f: C5H6 + O -> C5H5 + OH { A = 4.77E+04 n = 2.71 E = 4.63 }
2043 CP05f: C5H6 + OH -> C5H5 + H2O { A = 3.08E+06 n = 2.00 E = .00 }
2044 CP06f: C5H6 + O2 -> C5H5 + HO2 { A = 1.00E+14 n = .00 E = 155.44 }
2045 CP07f: C5H6 + HO2 -> C5H5 + H2O2 { A = 1.10E+04 n = 2.60 E = 53.97 }
2046 CP08f: C5H6 + CH3 -> C5H5 + CH4 { A = 1.80E-01 n = 4.00 E = .00 }
2047
2048 # From CH4 + ?? (x0.5)
2049 CP09f: C5H6 + C2H3 -> C5H5 + C2H4 { A = 5.55E+04 n = 2.02 E = 13.17 }
2050 CP10f: C5H6 + A-C3H5 -> C5H5 + C3H6 { A = 2.15E+01 n = 3.31 E = 106.79 }
2051 CP11f: C5H6 + N-C4H5 -> C5H5 + C4H6 { A = 7.30E+10 n = 0.76 E = 63.51 }
2052
2053
2054 # Cyclopentadienyl radical
2055 # ------------------------
2056
2057 # Moskaleva & Lin 2000
2058 # Knyazev & Slagle 2002
2059 CP16f: C3H3 + C2H2 -> C5H5 { A = 6.87E+55 n =-12.50 E = 175.80 }
2060
2061 # Melius, Colvin, Marinov, Pitz, & Senkan 1996
2062 # Sharma & Green 2009 - Rate fitted at P=1bar
2063 # PRODUCTS TO BE CHECKED - Should be benzene?
2064 CP17 : C5H5 + CH3 -> C5H4CH2 + 2H { A = 4.91E+31 n = -4.85 E = 103.65 }
2065
2066 # Murakami et al. 2003 - Total rate
2067 # Kislov & Mebel - Branching ratio
2068 CP18 : C5H5 + C5H5 -> A2-C10H8 + 2H { A = 6.39E+29 n = -4.03 E = 147.30 }
2069
2070 # Robinson & Lindstedt 2011
2071 # estimated
2072 CP19f: C5H5 + C5H5 -> C9H7 + CH3 { A = 2.50E+12 n = .00 E = 40.00 }
2073
2074 # Kislov & Mebel 2008 - Full entrance rate
2075 CP20 : C5H5 + C5H6 -> C9H8 + CH3 { A = 7.86E-01 n = 3.07 E = 23.97 }
2076
2077 # Robinson & Lindstedt 2011
2078 CP21f: C5H5 + O -> N-C4H5 + CO { A = 1.27E+14 n = 0.26 E = 16.50 }
2079 CP22f: C5H5 + OH -> C4H6 + CO { A = 8.53E+13 n = 0.25 E = 18.20 }
2080 CP23f: C5H5 + OH -> C5H5O + H { A = 1.11E+05 n = 1.90 E = 138.60 }
2081 CP24f: C5H5 + O2 -> C5H4O + OH { A = 9.11E+15 n = -2.21 E = 10.20 }
2082 CP25f: C5H5 + O2 -> C5H5O + O { A = 4.37E+03 n = 2.40 E = 211.50 }
2083 CP26f: C5H5 + HO2 -> C5H5O + OH { A = 6.86E+13 n = 0.25 E = 21.30 }
2084
2085
2086 # Cyclopentadienoxy radical
2087 # -------------------------
2088
2089 # Robinson & Lindstedt 2011
2090 CP27 : C5H5O -> C5H4O + H { A = 8.18E+16 n = -2.32 E = 36.50 }
2091 CP28 : C5H5O -> N-C4H5 + CO { A = 2.15E+64 n =-15.14 E = 278.00 }
2092
2093 # 1/3 rate from CH3O
2094 CP29f: C5H5O + H -> C5H4O + H2 { A = 6.67E+12 n = .00 E = .00 }
2095 CP30f: C5H5O + O -> C5H4O + OH { A = 3.33E+12 n = .00 E = .00 }
2096 CP31f: C5H5O + OH -> C5H4O + H2O { A = 1.67E+12 n = .00 E = .00 }
2097 CP32f: C5H5O + O2 -> C5H4O + HO2 { A = 7.22E+09 n = .00 E = 7.32 }
2098
2099
2100 # Cyclopentadienone
2101 # -----------------
2102
2103 # Wang & Brezinsky 1998
2104 # Ristori et al. 2001
2105 # (products guessed)
2106 CP33 : C5H4O -> 2 C2H2 + CO { A = 6.20E+41 n = -7.87 E = 413.00 }
2107 CP34 : C5H4O -> C4H4 + CO { A = 5.00E+11 n = .00 E = 221.80 }
2108
2109 # From C2H4+R, C3H6+H
2110 # (products guessed)
2111 CP35 : C5H4O + H -> C2H3 + C2H2 + CO { A = 2.67E+12 n = 0.47 E = 22.72 }
2112 CP36 : C5H4O + O -> C3H3 + HCO + CO { A = 1.02E+08 n = 1.66 E = 2.75 }
2113
2114
2115
2116 #==========================================================================#
2117 # #
2118 # "Detailed kinetic modeling of benzene and toluene oxidation #
2119 # at high temperatures" #
2120 # Zoran M. Djurisic - Master's Thesis #
2121 # http://diesel.me.berkeley.edu/~zoran/publications/2000_MS_Thesis/ #
2122 # #
2123 #==========================================================================#
2124
2125
2126 # Benzene
2127 # -------
2128
2129 # Miller & Klippenstein 2003 (1bar)
2130 # Updated to include HPL from Harding et al. 2005
2131 BN00f: A1-C6H6 -> A1--C6H5 + H { A = 1.29E+61 n =-12.48 E = 619.59 }
2132
2133 # Mebel & Lin 1997
2134 BN01f: A1-C6H6 + H -> A1--C6H5 + H2 { A = 6.02E+08 n = 1.80 E = 68.42 }
2135
2136 # Lindsted & Skevis 1994
2137 BN02f: A1-C6H6 + O -> A1--C6H5 + OH { A = 2.00E+13 n = .00 E = 61.50 }
2138
2139 # Seta, Nakajima & Miyoshi 2006
2140 BN03f: A1-C6H6 + OH -> A1--C6H5 + H2O { A = 2.34E+04 n = 2.68 E = 3.07 }
2141 BN04f: A1-C6H6 + OH -> A1OH-C6H6O + H { A = 1.32E+02 n = 3.25 E = 23.39 }
2142
2143 # From C2H4 + O2 (x1.5)
2144 # Hua, Ruscic, Wang 2005
2145 # Backward ~ 2e12
2146 BN05f: A1-C6H6 + O2 -> A1--C6H5 + HO2 { A = 4.34E+14 n = .00 E = 269.00 }
2147
2148 # Taatjes, Wang, et al. 2010
2149 # Refitted
2150 BN06f: A1-C6H6 + O -> A1O-C6H5O + H { A = 1.99E+07 n = 1.80 E = 16.63 }
2151 BN07f: A1-C6H6 + O -> A1OH-C6H6O { A = 1.53E+10 n = 0.92 E = 13.79 }
2152 BN08f: A1-C6H6 + O -> C5H6 + CO { A = 1.53E+17 n = -0.89 E = 64.89 }
2153
2154
2155 # Phenyl radical
2156 # --------------
2157
2158 # Wang et al. 2000
2159 BN09f: A1--C6H5 + M9 -> O-C6H4 + H + M9 { A = 1.00E+84 n =-18.87 E = 376.98
2160 Ai= 4.30E+12 ni= 0.62 Ei= 323.43
2161 fcA = 0.098 fctA = 696
2162 fcb = 0.902 fctb = 358
2163 fcc = 1.0 fctc = 3856 }
2164
2165 # da Silva, Chen & Bozzelli 2007
2166 # From 3/4-methylphenyl + O2
2167 BN10f: A1--C6H5 + O2 -> A1O-C6H5O + O { A = 8.57E+20 n = -2.27 E = 30.08 }
2168
2169 # Frank, Herzler, Just & Wahl 1994
2170 BN11f: A1--C6H5 + O2 -> OC6H4O + H { A = 3.00E+13 n = .00 E = 37.58 }
2171 BN12f: A1--C6H5 + O -> A1O-C6H5O { A = 1.00E+14 n = .00 E = .00 }
2172
2173 BN13f: A1--C6H5 + OH -> A1O-C6H5O + H { A = 3.00E+13 n = .00 E = .00 }
2174 BN14f: A1--C6H5 + HO2 -> A1O-C6H5O + OH { A = 3.00E+13 n = .00 E = .00 }
2175
2176 # Tokmakov & Lin 1999/2002
2177 BN15f: A1--C6H5 + CH4 -> A1-C6H6 + CH3 { A = 3.89E-03 n = 4.57 E = 22.00 }
2178
2179
2180 # Phenol
2181 # ------
2182
2183 # Xu & Lin 2006
2184 # Rates for 1 atm
2185 # Formation of CO x0.765 to better match Horn & Roy 1989
2186 BN16f: A1OH-C6H6O -> C5H6 + CO { A = 6.59E+15 n = -0.61 E = 310.11 }
2187 BN17f: A1OH-C6H6O -> A1O-C6H5O + H { A = 1.01E+71 n =-15.92 E = 522.12 }
2188
2189 # From CH3OH+R
2190 BN18f: A1OH-C6H6O + H -> A1O-C6H5O + H2 { A = 5.48E+06 n = 2.15 E = 46.44 }
2191 BN19f: A1OH-C6H6O + OH -> A1O-C6H5O + H2O { A = 5.71E+03 n = 2.62 E = -2.85 }
2192 BN20f: A1OH-C6H6O + CH3 -> A1O-C6H5O + CH4 { A = 2.31E+13 n = -0.48 E = 61.07 }
2193
2194 # Brezinsky et al. 1998
2195 #N21f: A1OH-C6H6O + O2 -> A1O-C6H5O + HO2 { A = 7.32E+13 n = .00 E = 173.22 }
2196
2197
2198 # Phenoxy radical
2199 # 2-B1 state for O=C6H5
2200 # ---------------------
2201
2202 # Murakami et al. 2003
2203 BN22f: A1O-C6H5O -> C5H5 + CO { A = 2.90E+10 n = .00 E = 152.40 }
2204
2205 # From C2H5 + O (x2)
2206 BN23f: A1O-C6H5O + O -> OC6H4O + H { A = 6.34E+13 n = 0.03 E = -1.65 }
2207
2208 # From A-C3H5 + O2 - Total rate (x3/2)
2209 BN24f: A1O-C6H5O + O2 -> OC6H4O + OH { A = 6.51E+07 n = 1.30 E = 73.92 }
2210
2211
2212 # p-Benzoquinone
2213 # Thermoprop & Reactions for para
2214 # -------------------------------
2215
2216 BN25 : OC6H4O -> C5H4O + CO { A = 7.40E+11 n = .00 E = 246.86 }
2217
2218 BN26 : OC6H4O + H -> C5H5O + CO { A = 4.30E+09 n = 1.45 E = 16.18 }
2219 BN27 : OC6H4O + O -> CH2CO + C2H2 + 2 CO { A = 3.00E+13 n = .00 E = 20.92 }
2220
2221
2222 # Benzyne
2223 # -------
2224
2225 # Wang, Laskin, Moriarty, Frenklach 2000
2226 BN28 : O-C6H4 -> C4H2 + C2H2 { A = 1.20E+18 n = -0.34 E = 367.48 }
2227
2228 # Wang & Frenklach 1997
2229 BN29f: N-C4H3 + C2H2 -> O-C6H4 + H { A = 6.90E+46 n =-10.01 E = 125.94 }
2230
2231 BN30 : O-C6H4 + OH -> C5H5 + CO { A = 1.00E+13 n = .00 E = .00 }
2232
2233
2234
2235 #==========================================================================#
2236 # #
2237 # Toluene chemistry #
2238 # #
2239 # Oehlschlaeger, Davidson & Hanson, Comb. Flame, 2006, 147, 195-208 #
2240 # #
2241 #==========================================================================#
2242
2243
2244 # Toluene / Benzyl decomposition
2245 # ------------------------------
2246
2247 # Tokmakov et al. 2001 (x1.2 to match exp.)
2248 # Sheen, Rosado-Reyes, Tsang 2013 (within 2%)
2249 T01f: A1CH3-C7H8 + H -> A1-C6H6 + CH3 { A = 2.31E+06 n = 2.17 E = 17.42 }
2250
2251 # Klippenstein et al. 2007
2252 # Almost indep or pressure => HPL
2253 T02f: A1CH3-C7H8 -> A1CH2-C7H7 + H { A = 1.56E+13 n = 0.68 E = 373.24 }
2254 T03f: A1CH3-C7H8 -> A1--C6H5 + CH3 { A = 4.35E+22 n = -1.73 E = 436.01 }
2255 # P=1bar - 1000K-2500K
2256 T04f: A1CH2-C7H7 + H -> A1--C6H5 + CH3 { A = 5.83E+67 n =-14.15 E = 285.89 }
2257
2258 # Assumed products. Other choices: C7H6 + H, c-C7H7
2259 # Rate from Oehlschlaeger et al. 2006 (1.5 atm)
2260 T05f: A1CH2-C7H7 -> C5H5 + C2H2 { A = 8.20E+14 n = .00 E = 337.55 }
2261
2262
2263 # Toluene
2264 # -------
2265
2266 # Oehlschlaeger et al. 2006 (1.5 atm)
2267 T06f: A1CH3-C7H8 + H -> A1CH2-C7H7 + H2 { A = 6.47E+00 n = 3.98 E = 14.16 }
2268
2269 # From C3H8+O (x0.5)
2270 T07f: A1CH3-C7H8 + O -> A1CH2-C7H7 + OH { A = 9.50E+04 n = 2.68 E = 15.55 }
2271
2272 # From A1+O (x5/6)
2273 T08f: A1CH3-C7H8 + O -> OA1CH3-C7H7O + H { A = 1.66E+07 n = 1.80 E = 16.63 }
2274 T09f: A1CH3-C7H8 + O -> HOA1CH3-C7H8O { A = 1.28E+10 n = 0.92 E = 13.79 }
2275
2276 # Seta, Nakajima & Miyoshi 2006
2277 # Better match with Vasudevan, Davidson & Hanson 2005
2278 T10f: A1CH3-C7H8 + OH -> A1CH2-C7H7 + H2O { A = 1.77E+05 n = 2.39 E = -2.52 }
2279 T11f: A1CH3-C7H8 + OH -> A1OH-C6H6O + CH3 { A = 7.83E+02 n = 2.88 E = 13.48 }
2280 T12f: A1CH3-C7H8 + OH -> HOA1CH3-C7H8O + H { A = 3.14E+01 n = 3.37 E = 19.75 }
2281
2282 # Oehlschlaeger et al. 2006 (1.5 atm)
2283 T13f: A1CH3-C7H8 + O2 -> A1CH2-C7H7 + HO2 { A = 2.18E+07 n = 2.50 E = 192.65 }
2284
2285 # Baulch et al. 2005
2286 T14f: A1CH3-C7H8 + HO2 -> A1CH2-C7H7 + H2O2 { A = 9.33E+04 n = 2.50 E = 61.44 }
2287
2288 # From C3H8+CH3 (x0.5)
2289 T15f: A1CH3-C7H8 + CH3 -> A1CH2-C7H7 + CH4 { A = 4.52E-01 n = 3.65 E = 29.93 }
2290
2291 # Heckmann, Hippler & Troe 1996
2292 T16f: A1CH3-C7H8 + A1--C6H5 -> A1CH2-C7H7 + A1-C6H6 { A = 7.94E+13 n = .00 E = 50.00 }
2293
2294
2295 # Benzyl radical
2296 # --------------
2297
2298 # da Silva & Bozzelli 2012 - P=1atm
2299 T17f: A1CH2-C7H7 + O -> A1-C6H6 + HCO { A = 6.98E+12 n = 0.33 E = 2.87 }
2300 T18f: A1CH2-C7H7 + O -> A1CHO-C7H6O + H { A = 2.75E+13 n = 0.07 E = 3.06 }
2301
2302 # Murakami et al. 2007 - HPL
2303 # Canneaux et al. 2008 - Benzylperoxy isomerization
2304 # Benzylperoxy in Steady State
2305 T19f: A1CH2-C7H7 + O2 -> A1CHO-C7H6O + OH { A = 3.76E+15 n = -1.55 E = 47.37 }
2306
2307 # da Silva & Bozzelli 2008
2308 T21f: A1CH2-C7H7 + HO2 -> A1CH2O-C7H7O + OH { A = 1.19E+09 n = 1.03 E = -9.41 }
2309
2310 # From A-C3H5
2311 T22 : A1CH2-C7H7 + C3H3 -> A2-C10H8 + 2H { A = 1.88E+38 n = -7.53 E = 99.91 }
2312
2313
2314 # Alcoxy Benzyl
2315 # -------------
2316
2317 # da Silva & Bozzelli 2009 - P=1atm
2318 T23f: A1CH2O-C7H7O -> A1CHO-C7H6O + H { A = 5.26E+28 n = -5.08 E = 93.09 }
2319 T24f: A1CH2O-C7H7O -> A1--C6H5 + CH2O { A = 7.21E+33 n = -6.21 E = 154.18 }
2320 T25f: A1CH2O-C7H7O -> A1-C6H6 + HCO { A = 2.37E+32 n = -6.10 E = 120.54 }
2321
2322 # Choi, Xia, Park, Lin 2000 - written as reverse
2323 T26f: A1CHO-C7H6O + H -> A1--C6H5 + CH2O { A = 7.38E+13 n = -0.10 E = 50.49 }
2324
2325 # From CH3O (x2/3)
2326 T27f: A1CH2O-C7H7O + H -> A1CHO-C7H6O + H2 { A = 1.33E+13 n = .00 E = .00 }
2327 T28f: A1CH2O-C7H7O + O -> A1CHO-C7H6O + OH { A = 6.67E+12 n = .00 E = .00 }
2328 T29f: A1CH2O-C7H7O + OH -> A1CHO-C7H6O + H2O { A = 3.33E+12 n = .00 E = .00 }
2329 T30f: A1CH2O-C7H7O + O2 -> A1CHO-C7H6O + HO2 { A = 4.11E+10 n = .00 E = 7.32 }
2330
2331
2332 # Benzaldehyde
2333 # ------------
2334
2335 # From CH3CHO
2336 # Grela & Colussi 1986 - Loss of H then loss of CO
2337 T31 : A1CHO-C7H6O -> A1--C6H5 + CO + H { A = 2.72E+22 n = -1.74 E = 361.33 }
2338
2339 # From CH3CHO
2340 T32 : A1CHO-C7H6O + H -> A1--C6H5 + CO + H2 { A = 1.31E+05 n = 2.58 E = 5.10 }
2341 T33 : A1CHO-C7H6O + O -> A1--C6H5 + CO + OH { A = 1.95E+13 n = .00 E = 14.81 }
2342 T34 : A1CHO-C7H6O + OH -> A1--C6H5 + CO + H2O { A = 9.70E+05 n = 2.11 E = -7.06 }
2343 T35 : A1CHO-C7H6O + CH3 -> A1--C6H5 + CO + CH4 { A = 1.55E+00 n = 3.70 E = 19.10 }
2344
2345
2346 # Cresol
2347 # All isomers lumped into meta
2348 # ----------------------------
2349
2350 # From A1OH/A1O
2351 T36f: HOA1CH3-C7H8O -> OA1CH3-C7H7O + H { A = 1.01E+71 n =-15.92 E = 522.12 }
2352 T37f: HOA1CH3-C7H8O + H -> OA1CH3-C7H7O + H2 { A = 5.48E+06 n = 2.15 E = 46.44 }
2353 T38f: HOA1CH3-C7H8O + O -> OA1CH3-C7H7O + OH { A = 1.30E+05 n = 2.50 E = 20.92 }
2354 T39f: HOA1CH3-C7H8O + OH -> OA1CH3-C7H7O + H2O { A = 5.71E+03 n = 2.62 E = -2.85 }
2355 T40f: HOA1CH3-C7H8O + CH3-> OA1CH3-C7H7O + CH4 { A = 2.31E+13 n = -0.48 E = 61.07 }
2356
2357 T41 : OA1CH3-C7H7O -> C5H4CH2 + CO + H { A = 2.90E+10 n = .00 E = 152.40 }
2358
2359
2360 # Methyl-phenyl
2361 # All isomers lumped into meta
2362 # ----------------------------
2363
2364 # From A1 (x0.65)
2365 # From symmetry should be x5/6
2366 # Seta, Nakajima & Miyoshi 2006 - Rate for OH - Same as A1 x0.65
2367 T42f: A1CH3-C7H8 -> A1CH3*-C7H7 + H { A = 8.39E+60 n =-12.48 E = 619.59 }
2368 T43f: A1CH3-C7H8 + H -> A1CH3*-C7H7 + H2 { A = 3.91E+08 n = 1.80 E = 68.42 }
2369 T44f: A1CH3-C7H8 + O -> A1CH3*-C7H7 + OH { A = 1.60E+13 n = .00 E = 61.50 }
2370 T45f: A1CH3-C7H8 + OH -> A1CH3*-C7H7 + H2O { A = 1.36E+04 n = 2.69 E = 2.59 }
2371 T46f: A1CH3-C7H8 + CH3 -> A1CH3*-C7H7 + CH4 { A = 1.79E-02 n = 4.46 E = 57.06 }
2372
2373 # From A1-
2374 T47f: A1CH3*-C7H7 + O -> OA1CH3-C7H7O { A = 1.00E+14 n = .00 E = .00 }
2375 T48f: A1CH3*-C7H7 + OH -> OA1CH3-C7H7O + H { A = 3.00E+13 n = .00 E = .00 }
2376 T49f: A1CH3*-C7H7 + HO2 -> OA1CH3-C7H7O + OH { A = 3.00E+13 n = .00 E = .00 }
2377
2378 # da Silva, Chen & Bozzelli 2007
2379 # Assumed products for methyloxepinoxy decomposition
2380 T50f: A1CH3*-C7H7 + O2 -> OA1CH3-C7H7O + O { A = 8.57E+20 n = -2.27 E = 30.08 }
2381 T51 : A1CH3*-C7H7 + O2 -> C5H4CH2 + CO2 + H { A = 2.55E+13 n = -0.44 E = -6.90 }
2382 T52 : A1CH3*-C7H7 + O2 -> P-C3H4 + C2H3 + 2CO { A = 2.55E+13 n = -0.44 E = -6.90 }
2383
2384
2385
2386 #===============================================================================#
2387 # #
2388 # Styrene Chemistry #
2389 # Adapted from C2H4 chemistry #
2390 # Additional rates from Kislov & Mebel 2005 #
2391 # #
2392 #===============================================================================#
2393
2394
2395 # Styrene
2396 # -------
2397
2398 # Greda et al. 1992
2399 ST01 : A1C2H3-C8H8 -> A1-C6H6 + H2C2 { A = 2.40E+14 n = .00 E = 326.90 }
2400
2401 # Wang & Frenklach 1997 - estimated HPL
2402 ST02f: A1--C6H5 + C2H3 -> A1C2H3-C8H8 { A = 6.00E+12 n = .00 E = .00 }
2403
2404 # Tokmakov & Lin 2004
2405 ST03f: A1--C6H5 + C2H4 -> A1C2H3-C8H8 + H { A = 3.62E+28 n = -4.24 E = 99.85 }
2406 ST04f: A1C2H3-C8H8 + H -> A1-C6H6 + C2H3 { A = 5.62E+24 n = -3.00 E = 82.97 }
2407
2408 # From A1CH3
2409 ST05f: A1C2H3-C8H8 + OH -> A1OH-C6H6O + C2H3 { A = 7.83E+02 n = 2.88 E = 13.48 }
2410
2411 # From C2H4 (x0.5)
2412 ST06f: A1C2H3-C8H8 -> A1C2H2-C8H7 + H { A = 3.01E+14 n = 0.34 E = 465.49 }
2413 ST07f: A1C2H3-C8H8 + H -> A1C2H2-C8H7 + H2 { A = 6.35E+04 n = 2.75 E = 48.74 }
2414 ST08f: A1C2H3-C8H8 + OH -> A1C2H2-C8H7 + H2O { A = 1.12E+04 n = 2.75 E = 9.27 }
2415
2416 # From A1 (x1/3)
2417 ST09f: A1C2H3-C8H8 -> A1C2H3*-C8H7 + H { A = 4.30E+60 n =-12.48 E = 619.59 }
2418 ST10f: A1C2H3-C8H8 + H -> A1C2H3*-C8H7 + H2 { A = 2.01E+08 n = 1.80 E = 68.42 }
2419 ST11f: A1C2H3-C8H8 + OH -> A1C2H3*-C8H7 + H2O { A = 7.80E+03 n = 2.68 E = 3.07 }
2420
2421 # From C2H4 (x0.5)
2422 # Half for each carbon atoms
2423 ST12f: A1C2H3-C8H8 + O -> A1CH2-C7H7 + HCO { A = 1.95E+08 n = 1.36 E = 3.71 }
2424 ST13f: A1C2H3-C8H8 + O -> A1CHO-C7H6O + T-CH2 { A = 3.58E+04 n = 2.47 E = 3.89 }
2425
2426
2427 # Styryl radical
2428 # --------------
2429
2430 # Tolkmakov & Lin 2003
2431 ST16f: A1--C6H5 + C2H2 -> A1C2H-C8H6 + H { A = 2.66E+32 n = -5.30 E = 99.52 }
2432 ST17f: A1--C6H5 + C2H2 -> A1C2H2-C8H7 { A = 4.80E+44 n = -9.90 E = 73.75 }
2433
2434 # Kislov & Mebel 2005 - HPL
2435 ST18f: A1C2H2-C8H7 -> A1C2H3*-C8H7 { A = 5.90E+10 n = 0.55 E = 115.34 }
2436
2437 # From N-C4H5
2438 ST19f: A1C2H2-C8H7 -> A1C2H-C8H6 + H { A = 1.81E+54 n =-12.69 E = 215.02 }
2439 ST20f: A1C2H2-C8H7 + H -> A1C2H-C8H6 + H2 { A = 1.50E+13 n = .00 E = .00 }
2440 ST21f: A1C2H2-C8H7 + OH -> A1C2H-C8H6 + H2O { A = 2.50E+12 n = .00 E = .00 }
2441 ST22f: A1C2H2-C8H7 + O2 -> A1C2H-C8H6 + HO2 { A = 6.70E+05 n = 1.61 E = -1.61 }
2442
2443 # From C2H3 + O
2444 ST23f: A1C2H2-C8H7 + O -> A1CH2-C7H7 + CO { A = 1.03E+13 n = 0.21 E = -1.79 }
2445
2446 # From C2H3 + O2
2447 ST24 : A1C2H2-C8H7 + O2 -> A1CH2-C7H7 + CO + O { A = 3.80E+11 n = 0.19 E = 0.20 }
2448 ST25f: A1C2H2-C8H7 + O2 -> A1CHO-C7H6O + HCO { A = 4.05E+17 n = -1.86 E = 4.88 }
2449 ST26 : A1C2H2-C8H7 + O2 -> A1CHO-C7H6O + CO + H { A = 2.22E+16 n = -1.35 E = 3.28 }
2450
2451
2452 # Ethynylbenzene
2453 # --------------
2454
2455 # Goulay & Leone 2006
2456 # Woon, Park & Jin-Young 2009
2457 ST27f: A1-C6H6 + C2H -> A1C2H-C8H6 + H { A = 2.00E+14 n = .00 E = .00 }
2458
2459 # From A1 (x1/3)
2460 ST28f: A1C2H-C8H6 -> A1C2H*-C8H5 + H { A = 4.30E+60 n =-12.48 E = 619.59 }
2461 ST29f: A1C2H-C8H6 + H -> A1C2H*-C8H5 + H2 { A = 2.01E+08 n = 1.80 E = 68.42 }
2462 ST30f: A1C2H-C8H6 + OH -> A1C2H*-C8H5 + H2O { A = 7.80E+03 n = 2.68 E = 3.07 }
2463
2464 # From C2H2
2465 ST31f: A1C2H-C8H6 + O -> A1--C6H5 + HCCO { A = 3.70E+09 n = 1.28 E = 10.34 }
2466
2467 ST32f: A1C2H-C8H6 + OH -> A1--C6H5 + CH2CO { A = 2.10E+01 n = 3.22 E = -1.76 }
2468 ST33f: A1C2H-C8H6 + OH -> A1CH2-C7H7 + CO { A = 6.40E+08 n = 0.73 E = 10.79 }
2469
2470
2471
2472 #==========================================================================#
2473 # #
2474 # Ethyl-Benzene chemistry #
2475 # #
2476 # Adapted from C3H8 and Toluene/Benzene chemistry #
2477 # #
2478 #==========================================================================#
2479
2480
2481 # Ethylbenzene
2482 # ------------
2483
2484 # Estimated from C3H7+H - HPL
2485 EB01f: A1C2H4-C8H9 + H -> A1C2H5-C8H10 { A = 3.61E+13 n = .00 E = .00 }
2486
2487 # Estimated from C2H5+CH3 - HPL
2488 EB02f: A1CH2-C7H7 + CH3 -> A1C2H5-C8H10 { A = 2.00E+13 n = .00 E = .00 }
2489 EB03f: A1--C6H5 + C2H5 -> A1C2H5-C8H10 { A = 2.00E+13 n = .00 E = .00 }
2490
2491 # From A1CH3
2492 EB04f: A1C2H5-C8H10 + H -> A1-C6H6 + C2H5 { A = 2.31E+06 n = 2.17 E = 17.42 }
2493 EB05f: A1C2H5-C8H10 + OH -> A1OH-C6H6O + C2H5 { A = 7.83E+02 n = 2.88 E = 13.48 }
2494
2495 # From C3H8 (x0.5)
2496 EB06f: A1C2H5-C8H10 + H -> A1C2H4-C8H9 + H2 { A = 4.68E+07 n = 1.97 E = 34.31 }
2497 EB07f: A1C2H5-C8H10 + O -> A1C2H4-C8H9 + OH { A = 9.95E+04 n = 2.68 E = 15.55 }
2498 EB08f: A1C2H5-C8H10 + OH -> A1C2H4-C8H9 + H2O { A = 2.67E+03 n = 2.94 E = -1.75 }
2499 EB09f: A1C2H5-C8H10 + CH3 -> A1C2H4-C8H9 + CH4 { A = 4.52E-01 n = 3.65 E = 29.93 }
2500 EB10f: A1C2H5-C8H10 + HO2 -> A1C2H4-C8H9 + H2O2 { A = 2.38E+04 n = 2.55 E = 69.00 }
2501
2502
2503 # N-Ethylbenzene radical
2504 # ----------------------
2505
2506 # Tokmakov & Lin 2004
2507 # HPL for both decompositions
2508 EB11f: A1C2H4-C8H9 -> A1--C6H5 + C2H4 { A = 1.72E+11 n = 0.78 E = 161.94 }
2509 EB12f: A1C2H4-C8H9 -> A1C2H3-C8H8 + H { A = 3.79E+06 n = 1.99 E = 134.33 }
2510
2511 # From N-C3H7
2512 EB13f: A1C2H4-C8H9 + O -> A1CH2-C7H7 + CH2O { A = 9.60E+13 n = .00 E = .00 }
2513
2514 # From N-C3H7
2515 EB14f: A1C2H4-C8H9 + H -> A1C2H3-C8H8 + H2 { A = 1.80E+12 n = .00 E = .00 }
2516 EB15f: A1C2H4-C8H9 + OH -> A1C2H3-C8H8 + H2O { A = 2.41E+13 n = .00 E = .00 }
2517 EB16f: A1C2H4-C8H9 + CH3 -> A1C2H3-C8H8 + CH4 { A = 3.31E+12 n = .00 E = -3.22 }
2518
2519 # Altarawneh, Dlugogorski, Kennedy, Mackie 2013
2520 EB17f: A1C2H4-C8H9 + O2 -> A1C2H3-C8H8 + HO2 { A = 3.08E+13 n = .00 E = 75.66 }
2521
2522 # From NC7
2523 EB18 : A1C2H4-C8H9 + HO2 -> A1CH2-C7H7 + CH2O + OH{ A = 7.00E+12 n = .00 E = -4.18 }
2524
2525
2526 #=========================================================================#
2527 # #
2528 # Xylene Oxidation Chemistry #
2529 # Adapted from Toluene Chemistry #
2530 # #
2531 #=========================================================================#
2532
2533
2534 # Xylene
2535 # ------
2536
2537 # From A1CH3 (x2)
2538 XY01f: A1CH3CH3-C8H10 -> A1CH3CH2-C8H9 + H { A = 2.12E+13 n = 0.68 E = 373.24 }
2539 XY02f: A1CH3CH3-C8H10 -> A1CH3*-C7H7 + CH3 { A = 8.70E+22 n = -1.73 E = 436.01 }
2540
2541 # From A1CH3+R (x2)
2542 XY03f: A1CH3CH3-C8H10 + H -> A1CH3CH2-C8H9 + H2 { A = 1.29E+01 n = 3.98 E = 14.16 }
2543 XY04f: A1CH3CH3-C8H10 + O -> A1CH3CH2-C8H9 + OH { A = 1.90E+05 n = 2.68 E = 15.55 }
2544 XY05f: A1CH3CH3-C8H10 + OH -> A1CH3CH2-C8H9 + H2O { A = 3.54E+05 n = 2.39 E = -2.52 }
2545 XY06f: A1CH3CH3-C8H10 + O2 -> A1CH3CH2-C8H9 + HO2 { A = 4.36E+07 n = 2.50 E = 192.65 }
2546 XY07f: A1CH3CH3-C8H10 + HO2 -> A1CH3CH2-C8H9 + H2O2 { A = 1.87E+05 n = 2.50 E = 61.44 }
2547 XY08f: A1CH3CH3-C8H10 + CH3 -> A1CH3CH2-C8H9 + CH4 { A = 9.03E-01 n = 3.65 E = 29.93 }
2548
2549 # From A1CH3+X (x2)
2550 XY09f: A1CH3CH3-C8H10 + H -> A1CH3-C7H8 + CH3 { A = 4.62E+06 n = 2.17 E = 17.42 }
2551 XY10f: A1CH3CH3-C8H10 + OH -> HOA1CH3-C7H8O + CH3 { A = 1.57E+03 n = 2.88 E = 13.48 }
2552
2553 # !!!! CAREFUL !!!!
2554 # Path from Bounaceur et al. 2005
2555 # Rate from A1+O (x2/3)
2556 XY11 : A1CH3CH3-C8H10 + O -> A1CH3-C7H8 + CO + 2H { A = 1.82E+08 n = 1.55 E = 12.93 }
2557
2558
2559 # Xylyl radical
2560 # -------------
2561
2562 # Path from Bournaceur et al. 2005
2563 # Rate from A1CH2
2564 XY12 : A1CH3CH2-C8H9 -> A1-C6H6 + H + C2H2 { A = 8.20E+14 n = .00 E = 337.55 }
2565
2566 XY13f: A1CH3CH2-C8H9 + H -> A1CH3*-C7H7 + CH3 { A = 5.83E+67 n =-14.15 E = 285.89 }
2567
2568 # From A1CH2+O
2569 XY14f: A1CH3CH2-C8H9 + O -> A1CH3CHO-C8H8O + H { A = 2.75E+13 n = 0.07 E = 3.06 }
2570 XY15f: A1CH3CH2-C8H9 + O -> A1CH3-C7H8 + HCO { A = 6.98E+12 n = 0.33 E = 2.87 }
2571
2572 # From A1CH2+O2
2573 # Addition from Murakami et al. 2009
2574 # Peroxy isomerization from Canneaux et al. 2008
2575 XY16f: A1CH3CH2-C8H9 + O2 -> A1CH3CHO-C8H8O + OH { A = 1.38E+02 n = 2.42 E = 31.13 }
2576
2577 # From A1CH2+HO2
2578 # Assumed unique decomposition into A1CHO+H
2579 XY19 : A1CH3CH2-C8H9 + HO2 -> A1CH3CHO-C8H8O + H + OH { A = 1.19E+09 n = 1.03 E = -9.41 }
2580
2581 # From A-C3H5 + C3H3
2582 XY20 : A1CH3CH2-C8H9 + C3H3 -> A2CH3-C11H10 + 2H { A = 1.88E+38 n = -7.53 E = 99.91 }
2583
2584
2585 # Tolualdehyde
2586 # ------------
2587
2588 # From A1CH3 & CH3CHO decomposition
2589 XY21f: A1CH3CHO-C8H8O -> A1CHOCH2-C8H7O + H { A = 1.56E+13 n = 0.68 E = 373.24 }
2590 XY22 : A1CH3CHO-C8H8O -> A1--C6H5 + CO + CH3 { A = 4.35E+22 n = -1.73 E = 436.01 }
2591 XY23 : A1CH3CHO-C8H8O -> A1CH3*-C7H7 + CO + H { A = 2.72E+22 n = -1.74 E = 361.33 }
2592
2593 # From A1CH3+R
2594 XY24f: A1CH3CHO-C8H8O + H -> A1CHOCH2-C8H7O + H2 { A = 6.47E+00 n = 3.98 E = 14.16 }
2595 XY25f: A1CH3CHO-C8H8O + O -> A1CHOCH2-C8H7O + OH { A = 9.50E+04 n = 2.68 E = 15.55 }
2596 XY26f: A1CH3CHO-C8H8O + OH -> A1CHOCH2-C8H7O + H2O { A = 1.77E+05 n = 2.39 E = -2.52 }
2597 XY27f: A1CH3CHO-C8H8O + CH3 -> A1CHOCH2-C8H7O + CH4 { A = 4.52E-01 n = 3.65 E = 29.93 }
2598
2599 # From CH3CHO+R
2600 XY28 : A1CH3CHO-C8H8O + H -> A1CH3*-C7H7 + CO + H2 { A = 1.31E+05 n = 2.58 E = 5.10 }
2601 XY29 : A1CH3CHO-C8H8O + O -> A1CH3*-C7H7 + CO + OH { A = 1.95E+13 n = .00 E = 14.81 }
2602 XY30 : A1CH3CHO-C8H8O + OH -> A1CH3*-C7H7 + CO + H2O { A = 9.70E+05 n = 2.11 E = -7.06 }
2603 XY31 : A1CH3CHO-C8H8O + CH3 -> A1CH3*-C7H7 + CO + CH4 { A = 1.55E+00 n = 3.70 E = 19.10 }
2604
2605
2606 # Tolualdehyde radical
2607 # --------------------
2608
2609 # From A1CH2+O
2610 XY32f: A1CHOCH2-C8H7O + O -> A1CHOCHO-C8H6O2 + H { A = 2.75E+13 n = 0.07 E = 3.06 }
2611 XY33f: A1CHOCH2-C8H7O + O -> A1CHO-C7H6O + HCO { A = 6.98E+12 n = 0.33 E = 2.87 }
2612
2613 # From A1CH2+HO2
2614 # Assumed unique decomposition into A1CHO+H
2615 XY33 : A1CHOCH2-C8H7O + HO2 -> A1CHOCHO-C8H6O2 + H + OH { A = 1.19E+09 n = 1.03 E = -9.41 }
2616
2617
2618 # Phthalaldehyde
2619 # --------------
2620
2621 # From CH3CHO decomposition (x2)
2622 XY34 : A1CHOCHO-C8H6O2 -> A1--C6H5 + 2 CO + H { A = 5.44E+22 n = -1.74 E = 361.33 }
2623
2624 # From CH3CHO+R (x2)
2625 XY35 : A1CHOCHO-C8H6O2 + H -> A1CHO-C7H6O + CO + H { A = 2.62E+05 n = 2.58 E = 5.10 }
2626 XY36 : A1CHOCHO-C8H6O2 + O -> A1CHO-C7H6O + CO + O { A = 3.90E+13 n = .00 E = 14.81 }
2627 XY37 : A1CHOCHO-C8H6O2 + OH -> A1CHO-C7H6O + CO + OH { A = 1.94E+06 n = 2.11 E = -7.06 }
2628 XY38 : A1CHOCHO-C8H6O2 + CH3 -> A1CHO-C7H6O + CO + CH3 { A = 3.10E+00 n = 3.70 E = 19.10 }
2629
2630
2631
2632 #==========================================================================#
2633 # #
2634 # Indene chemistry #
2635 # Adapted from Cyclopentadiene #
2636 # #
2637 #==========================================================================#
2638
2639
2640 # Indene
2641 # ------
2642
2643 # Kislov & Mebel 2007
2644 # Rate estimated
2645 I00f: A1--C6H5 + C3H3 -> C9H8 { A = 1.00E+13 n = .00 E = .00 }
2646
2647 # Kislov & Mebel 2007
2648 I01f: A1CH2-C7H7 + C2H2 -> C9H8 + H { A = 3.16E+04 n = 2.48 E = 46.28 }
2649
2650 I02f: C9H8 -> C9H7 + H { A = 3.24E+49 n =-10.01 E = 423.40 }
2651 I03f: C9H8 + H -> C9H7 + H2 { A = 8.59E+07 n = 1.85 E = 13.97 }
2652
2653 I05f: C9H8 + O -> C9H7 + OH { A = 4.77E+04 n = 2.71 E = 4.63 }
2654 I06f: C9H8 + OH -> C9H7 + H2O { A = 3.08E+06 n = 2.00 E = .00 }
2655 I07f: C9H8 + O2 -> C9H7 + HO2 { A = 1.00E+14 n = .00 E = 155.44 }
2656 I08f: C9H8 + HO2 -> C9H7 + H2O2 { A = 1.10E+04 n = 2.60 E = 53.97 }
2657 I09f: C9H8 + CH3 -> C9H7 + CH4 { A = 1.80E-01 n = 4.00 E = .00 }
2658
2659 # From C2H4 + O
2660 #I10 : C9H8 + O -> O-C6H4 + C2H3 + CO + H { A = 1.02E+08 n = 1.66 E = 2.75 }
2661
2662
2663 # Indenyl radical
2664 # 2/5 of the rate for C5H5
2665 # ------------------------
2666
2667 I12 : C9H7 + C5H5 -> A3-C14H10 + 2H { A = 2.56E+29 n = -4.03 E = 147.30 }
2668 I13 : C9H7 + CH3 -> A2-C10H8 + 2H { A = 1.96E+31 n = -4.85 E = 103.65 }
2669
2670 # TEST - GB
2671 #I14 : C9H7 -> C5H5 + C4H2 { A = 1.00E+10 n= .00 E = 250.00 }
2672
2673 I15 : C9H7 + O -> A1C2H2-C8H7 + CO { A = 5.08E+13 n = 0.26 E = 16.50 }
2674 I16 : C9H7 + OH -> A1C2H3-C8H8 + CO { A = 3.41E+13 n = 0.25 E = 18.20 }
2675 I17 : C9H7 + OH -> C9H6O + 2H { A = 4.44E+04 n = 1.90 E = 138.60 }
2676 I18 : C9H7 + O2 -> C9H6O + OH { A = 3.64E+15 n = -2.21 E = 10.20 }
2677 I19 : C9H7 + O2 -> C9H6O + O + H { A = 1.75E+03 n = 2.40 E = 211.50 }
2678 I20 : C9H7 + HO2 -> C9H6O + OH + H { A = 2.74E+13 n = 0.25 E = 21.30 }
2679
2680 # From A-C3H5 + C3H3
2681 I21 : C9H7 + C3H3 -> A2R5-C12H8 + 2H { A = 1.88E+38 n = -7.53 E = 99.91 }
2682
2683
2684 # Indenone
2685 # --------
2686
2687 I22 : C9H6O -> O-C6H4 + C2H2 + CO { A = 6.20E+41 n = -7.87 E = 413.00 }
2688
2689 I23 : C9H6O + H -> A1C2H2-C8H7 + CO { A = 1.37E+09 n = 1.46 E = 5.67 }
2690 I24 : C9H6O + O -> O-C6H4 + CH2CO + CO { A = 1.02E+08 n = 1.66 E = 2.75 }
2691
2692
2693
2694 #==========================================================================#
2695 # #
2696 # Napthalene Oxidation Chemistry #
2697 # Adapted from Benzene #
2698 # #
2699 #==========================================================================#
2700
2701 # Naphthalene
2702 # 5/3 of the rate for A1
2703 # ----------------------
2704
2705 NP01f: A2-C10H8 -> A2--C10H7 + H { A = 8.60E+60 n =-12.48 E = 619.55 }
2706 NP02f: A2-C10H8 + H -> A2--C10H7 + H2 { A = 4.01E+08 n = 1.80 E = 68.42 }
2707 NP03f: A2-C10H8 + OH -> A2--C10H7 + H2O { A = 3.90E+04 n = 2.68 E = 3.07 }
2708
2709 NP04f: A2-C10H8 -> A2*-C10H7 + H { A = 8.60E+60 n =-12.48 E = 619.55 }
2710 NP05f: A2-C10H8 + H -> A2*-C10H7 + H2 { A = 4.01E+08 n = 1.80 E = 68.42 }
2711 NP06f: A2-C10H8 + OH -> A2*-C10H7 + H2O { A = 3.90E+04 n = 2.68 E = 3.07 }
2712
2713 NP07f: A2-C10H8 + O -> A2O-C10H7O + H { A = 3.32E+07 n = 1.80 E = 16.63 }
2714 NP08f: A2-C10H8 + O -> A2OH-C10H8O { A = 2.55E+10 n = 0.92 E = 13.79 }
2715 NP09f: A2-C10H8 + O -> C9H8 + CO { A = 2.55E+17 n = -0.89 E = 64.89 }
2716
2717 NP10f: A2-C10H8 + OH -> A2OH-C10H8O + H { A = 2.20E+02 n = 3.25 E = 23.39 }
2718
2719
2720 # Naphthyl radical
2721 # Full rate for A1-
2722 # -----------------
2723
2724 # Park, Nguyen, Xu, Lin 2009
2725 NP11f: A2--C10H7 -> A2*-C10H7 { A = 1.51E+07 n = .00 E = 184.85 }
2726
2727 NP12f: A2--C10H7 + O2 -> A2O-C10H7O + O { A = 8.57E+20 n = -2.27 E = 30.08 }
2728 NP13f: A2*-C10H7 + O2 -> A2O-C10H7O + O { A = 8.57E+20 n = -2.27 E = 30.08 }
2729
2730 NP14 : A2--C10H7 + O2 -> C9H6O + CO + H { A = 3.00E+13 n = .00 E = 37.58 }
2731 NP15 : A2*-C10H7 + O2 -> C9H6O + CO + H { A = 3.00E+13 n = .00 E = 37.58 }
2732
2733 NP16f: A2--C10H7 + O -> A2O-C10H7O { A = 1.00E+14 n = .00 E = .00 }
2734 NP17f: A2*-C10H7 + O -> A2O-C10H7O { A = 1.00E+14 n = .00 E = .00 }
2735
2736 NP18f: A2--C10H7 + OH -> A2O-C10H7O + H { A = 3.00E+13 n = .00 E = .00 }
2737 NP19f: A2*-C10H7 + OH -> A2O-C10H7O + H { A = 3.00E+13 n = .00 E = .00 }
2738
2739
2740 # Naphthol
2741 # Full rate for A1OH
2742 # ------------------
2743
2744 NP20f: A2OH-C10H8O -> C9H8 + CO { A = 8.62E+15 n = -0.61 E = 310.11 }
2745 NP21f: A2OH-C10H8O -> A2O-C10H7O + H { A = 1.01E+71 n =-15.92 E = 522.12 }
2746
2747 NP22f: A2OH-C10H8O + H -> A2O-C10H7O + H2 { A = 6.83E+01 n = 3.40 E = 30.26 }
2748 NP23f: A2OH-C10H8O + OH -> A2O-C10H7O + H2O { A = 1.73E+01 n = 3.40 E = -4.78 }
2749 NP24f: A2OH-C10H8O + CH3 -> A2O-C10H7O + CH4 { A = 3.70E-04 n = 4.70 E = 20.20 }
2750
2751
2752 # Naphthoxy radical
2753 # Full rate for A1O
2754 # -----------------
2755
2756 NP25f: A2O-C10H7O -> C9H7 + CO { A = 2.90E+10 n = .00 E = 152.40 }
2757 NP26 : A2O-C10H7O + O -> C9H6O + CO + H { A = 1.68E+14 n = .00 E = .00 }
2758 NP27 : A2O-C10H7O + O2 -> C9H6O + CO + OH { A = 6.51E+07 n = 1.30 E = 73.92 }
2759
2760
2761
2762 #=========================================================================#
2763 # #
2764 # alpha-MethylNaphthalene chemistry #
2765 # Adapted from Toluene chemistry #
2766 # #
2767 #=========================================================================#
2768
2769
2770 # MethylNaphthalene
2771 # -----------------
2772
2773 MN01f: A2CH3-C11H10 + H -> A2-C10H8 + CH3 { A = 2.31E+06 n = 2.17 E = 17.42 }
2774 MN02f: A2CH3-C11H10 + OH -> A2OH-C10H8O + CH3 { A = 7.83E+02 n = 2.88 E = 13.48 }
2775
2776 # Collision Limit at 298K
2777 MN03f: A2CH3-C11H10 -> A2CH2-C11H9 + H { A = 1.25E+18 n = -0.60 E = 396.59 }
2778 MN04f: A2CH3-C11H10 -> A2--C10H7 + CH3 { A = 3.20E+34 n = -5.02 E = 478.03 }
2779
2780 MN05f: A2CH2-C11H9 + H -> A2--C10H7 + CH3 { A = 5.83E+67 n =-14.15 E = 285.89 }
2781 MN06f: A2CH2-C11H9 -> C9H7 + C2H2 { A = 8.20E+14 n = .00 E = 337.55 }
2782
2783 MN07f: A2CH3-C11H10 + H -> A2CH2-C11H9 + H2 { A = 6.47E+00 n = 3.98 E = 14.16 }
2784 MN08f: A2CH3-C11H10 + O -> A2CH2-C11H9 + OH { A = 1.18E+00 n = 4.09 E = 10.65 }
2785 MN09f: A2CH3-C11H10 + OH -> A2CH2-C11H9 + H2O { A = 1.77E+05 n = 2.39 E = -2.52 }
2786 MN10f: A2CH3-C11H10 + O2 -> A2CH2-C11H9 + HO2 { A = 2.18E+07 n = 2.50 E = 192.65 }
2787 MN11f: A2CH3-C11H10 + CH3 -> A2CH2-C11H9 + CH4 { A = 1.73E+01 n = 3.44 E = 43.47 }
2788 MN12f: A2CH3-C11H10 + HO2 -> A2CH2-C11H9 + H2O2 { A = 9.33E+04 n = 2.50 E = 61.44 }
2789
2790 MN13 : A2CH3-C11H10 + O -> A2-C10H8 + CO + 2 H { A = 1.10E+13 n = .00 E = 18.96 }
2791 MN14 : A2CH3-C11H10 + O -> C9H7 + CH3 + CO { A = 1.47E+13 n = .00 E = 18.96 }
2792
2793
2794 # Methylene-Naphthyl
2795 # ------------------
2796
2797 MN15f: A2CH2-C11H9 + O -> A2-C10H8 + HCO { A = 6.98E+12 n = 0.33 E = 2.87 }
2798 MN16f: A2CH2-C11H9 + O -> A2CHO-C11H8O + H { A = 2.75E+13 n = 0.07 E = 3.06 }
2799 MN17f: A2CH2-C11H9 + O2 -> A2CHO-C11H8O + OH { A = 3.76E+15 n = -1.55 E = 47.37 }
2800 MN18f: A2CH2-C11H9 + HO2 -> A2CH2O-C11H9O + OH { A = 1.19E+09 n = 1.03 E = -9.41 }
2801
2802 MN19 : A2CH2-C11H9 + C3H3 -> A3-C14H10 + 2H { A = 1.88E+38 n = -7.53 E = 99.91 }
2803
2804
2805 # Methoxy-Naphthyl
2806 # ----------------
2807
2808 MN20f: A2CH2O-C11H9O -> A2CHO-C11H8O + H { A = 5.26E+28 n = -5.08 E = 93.09 }
2809 MN21f: A2CH2O-C11H9O -> A2--C10H7 + CH2O { A = 7.21E+33 n = -6.21 E = 154.18 }
2810
2811 MN22f: A2CH2O-C11H9O + H -> A2CHO-C11H8O + H2 { A = 1.33E+13 n = .00 E = .00 }
2812 MN23f: A2CH2O-C11H9O + O -> A2CHO-C11H8O + OH { A = 6.67E+12 n = .00 E = .00 }
2813 MN24f: A2CH2O-C11H9O + OH -> A2CHO-C11H8O + H2O { A = 3.33E+12 n = .00 E = .00 }
2814 MN25f: A2CH2O-C11H9O + O2 -> A2CHO-C11H8O + HO2 { A = 4.11E+10 n = .00 E = 7.32 }
2815
2816
2817 # Naphthaldehyde
2818 # --------------
2819
2820 MN26 : A2CHO-C11H8O -> A2--C10H7 + CO + H { A = 2.72E+22 n = -1.74 E = 361.33 }
2821
2822 MN27 : A2CHO-C11H8O + H -> A2--C10H7 + CO +H2 { A = 1.31E+05 n = 2.58 E = 5.10 }
2823 MN28 : A2CHO-C11H8O + O -> A2--C10H7 + CO +OH { A = 1.95E+13 n = .00 E = 14.81 }
2824 MN29 : A2CHO-C11H8O + OH -> A2--C10H7 + CO +H2O { A = 9.70E+05 n = 2.11 E = -7.06 }
2825 MN30 : A2CHO-C11H8O + CH3-> A2--C10H7 + CO +CH4 { A = 1.55E+00 n = 3.70 E = 19.10 }
2826
2827
2828
2829 #==========================================================================#
2830 # #
2831 # PAH chemistry #
2832 # HACA Based Mechanism #
2833 # #
2834 #==========================================================================#
2835
2836 # Fulvene
2837 # -------
2838
2839 # Jasper & Hansen 2013 - 1atm
2840 P01f: C5H4CH2 + H -> A1-C6H6 + H { A = 1.14E+32 n = -4.88 E = 79.05 }
2841
2842 # Senosiain & Miller 2007 (JPCA)
2843 P02f: N-C4H5 + C2H2 -> C5H4CH2 + H { A = 4.62E+15 n = -0.89 E = 38.25 }
2844 P03f: I-C4H5 + C2H2 -> C5H4CH2 + H { A = 6.80E+24 n = -3.45 E = 85.09 }
2845
2846 # Miller & Klippenstein 2003
2847 P04f: C5H4CH2 -> A1-C6H6 { A = 1.45E+45 n = -8.90 E = 405.86 }
2848 P05f: C5H4CH2 -> A1--C6H5 + H { A = 2.24E+68 n =-14.65 E = 596.54 }
2849
2850
2851 # Benzene
2852 # -------
2853
2854 # Wang & Frenklach 1997
2855 P06f: N-C4H3 + C2H2 -> A1--C6H5 { A = 9.60E+70 n =-17.77 E = 130.96 }
2856
2857 # Senosiain & Miller 2007 (JPCA)
2858 P07f: N-C4H5 + C2H2 -> A1-C6H6 + H { A = 1.38E+16 n = -1.00 E = 37.24 }
2859 P08f: I-C4H5 + C2H2 -> A1-C6H6 + H { A = 1.67E+23 n = -3.30 E = 104.43 }
2860
2861 # Miller, Klippenstein, Georgievskii, Harding, Allen, Simmonett 2010
2862 P09 : A-C3H5 + C3H3 -> C5H4CH2 + 2H { A = 1.88E+38 n = -7.53 E = 99.91 }
2863
2864 # Georgievskii, Miller, & Klippenstein 2007
2865 # -> Total rate at 1bar
2866 # Miller & Klippenstein 2003
2867 # -> Branching ratios
2868 # -> 2-ethynyl-1,3-butadiene lumped into Fulvene
2869 # Fitted rates valid for 800K-2000K - P=1bar
2870 P10f: C3H3 + C3H3 -> C5H4CH2 { A = 8.25E+46 n =-10.10 E = 70.96 }
2871 P11f: C3H3 + C3H3 -> A1-C6H6 { A = 1.07E+45 n = -9.57 E = 71.19 }
2872 P12f: C3H3 + C3H3 -> A1--C6H5 + H { A = 5.77E+37 n = -7.00 E = 131.82 }
2873
2874 # Tokmakov & Lin 2004
2875 P13f: A1--C6H5 + C2H4 -> A1-C6H6 + C2H3 { A = 9.45E-03 n = 4.47 E = 18.71 }
2876
2877
2878 # Naphthalene
2879 # -----------
2880
2881 # From A1 (x1/3)
2882 P14f: A1C2H-C8H6 + C2H -> A2--C10H7 { A = 6.67E+13 n = .00 E = .00 }
2883 P15f: A1C2H3-C8H8 + C2H -> A2-C10H8 + H { A = 6.67E+13 n = .00 E = .00 }
2884
2885 # Kislov & Mebel 2005
2886 P16f: A1C2H*-C8H5 + C2H2 -> A2--C10H7 { A = 1.34E+04 n = 2.50 E = 5.37 }
2887 P17f: A1C2H2-C8H7 + C2H2 -> A2-C10H8 + H { A = 2.62E+06 n = 2.00 E = 19.16 }
2888 P18f: A1C2H3*-C8H7 + C2H2 -> A2-C10H8 + H { A = 3.02E+03 n = 2.55 E = 13.31 }
2889
2890 # From A1 (x1/3)
2891 P19f: A1C2H-C8H6 + C2H3 -> A2-C10H8 + H { A = 4.50E+16 n = -1.15 E = 61.01 }
2892
2893 # From A1-
2894 P20f: A1C2H*-C8H5 + C2H4 -> A2-C10H8 + H { A = 3.62E+28 n = -4.24 E = 99.85 }
2895
2896 # Aguilera-Iparraguirre & Klopper 2007
2897 # Total entrance channel rate
2898 P21f: A1--C6H5 + C4H4 -> A2-C10H8 + H { A = 1.26E+04 n = 2.61 E = 6.00 }
2899
2900
2901 # From A1 (x2/3)
2902 P22f: A2-C10H8 + C2H -> A2C2HA-C12H8 + H { A = 1.67E+14 n = .00 E = .00 }
2903 P23f: A2-C10H8 + C2H -> A2C2HB-C12H8 + H { A = 1.67E+14 n = .00 E = .00 }
2904
2905 # Park, Nguyen, Xu, Lin 2009
2906 P24f: A2--C10H7 + C2H2 -> A2R5-C12H8 + H { A = 2.81E+07 n = 1.77 E = 9.37 }
2907 P25f: A2*-C10H7 + C2H2 -> A2C2HB-C12H8 + H { A = 5.38E+07 n = 1.65 E = 10.71 }
2908
2909 # From A1 (x2/3)
2910 P26f: A2-C10H8 + C2H3 -> A2C2H2A-C12H9 + H2 { A = 9.01E+16 n = -1.15 E = 61.01 }
2911 P27f: A2-C10H8 + C2H3 -> A2C2H2B-C12H9 + H2 { A = 9.01E+16 n = -1.15 E = 61.01 }
2912
2913 # From A1-
2914 P28f: A2--C10H7 + C2H4 -> A2C2H2A-C12H9 + H2 { A = 3.62E+28 n = -4.24 E = 99.85 }
2915 P29f: A2*-C10H7 + C2H4 -> A2C2H2B-C12H9 + H2 { A = 3.62E+28 n = -4.24 E = 99.85 }
2916
2917
2918 # From A1C2H2
2919 P30f: A2C2H2A-C12H9 -> A2C2HA-C12H8 + H { A = 1.81E+54 n =-12.69 E = 215.02 }
2920 P31f: A2C2H2A-C12H9 + H -> A2C2HA-C12H8 + H2 { A = 1.50E+13 n = .00 E = .00 }
2921 P32f: A2C2H2A-C12H9 + OH -> A2C2HA-C12H8 + H2O { A = 2.50E+12 n = .00 E = .00 }
2922
2923 P33f: A2C2H2B-C12H9 -> A2C2HB-C12H8 + H { A = 1.81E+54 n =-12.69 E = 215.02 }
2924 P34f: A2C2H2B-C12H9 + H -> A2C2HB-C12H8 + H2 { A = 1.50E+13 n = .00 E = .00 }
2925 P35f: A2C2H2B-C12H9 + OH -> A2C2HB-C12H8 + H2O { A = 2.50E+12 n = .00 E = .00 }
2926
2927 # From A1 (x1/6)
2928 P36f: A2C2HA-C12H8 -> A2C2HA*-C12H7 + H { A = 2.15E+60 n =-12.48 E = 619.55 }
2929 P37f: A2C2HA-C12H8 + H -> A2C2HA*-C12H7 + H2 { A = 1.00E+08 n = 1.80 E = 68.42 }
2930 P38f: A2C2HA-C12H8 + OH -> A2C2HA*-C12H7 + H2O { A = 3.90E+03 n = 2.68 E = 3.07 }
2931
2932 P39f: A2C2HB-C12H8 -> A2C2HB*-C12H7 + H { A = 2.15E+60 n =-12.48 E = 619.55 }
2933 P40f: A2C2HB-C12H8 + H -> A2C2HB*-C12H7 + H2 { A = 1.00E+08 n = 1.80 E = 68.42 }
2934 P41f: A2C2HB-C12H8 + OH -> A2C2HB*-C12H7 + H2O { A = 3.90E+03 n = 2.68 E = 3.07 }
2935
2936
2937 # Acenaphthalene
2938 # --------------
2939
2940 # Kislov & Mebel 2005
2941 P42f: A2C2H2A-C12H9 -> A2R5-C12H8 + H { A = 2.88E+11 n = 0.23 E = 71.24 }
2942
2943 # Lifshitz, Tambura & Dubnikova 2007
2944 P43f: A2C2HA-C12H8 + H -> A2R5-C12H8 + H { A = 3.52E+12 n = .00 E = 55.90 }
2945
2946 # From A1 (x2/3)
2947 P44f: A2R5-C12H8 -> A2R5--C12H7 + H { A = 8.60E+60 n =-12.48 E = 619.55 }
2948 P45f: A2R5-C12H8 + H -> A2R5--C12H7 + H2 { A = 4.01E+08 n = 1.80 E = 68.42 }
2949 P46f: A2R5-C12H8 + OH -> A2R5--C12H7 + H2O { A = 1.34E+04 n = 2.68 E = 3.07 }
2950
2951
2952 # From A1 (x2/3)
2953 P47f: A2R5-C12H8 + C2H -> A2R5C2H-C14H8 + H { A = 1.67E+14 n = .00 E = .00 }
2954
2955 # From A2*
2956 P48f: A2R5--C12H7 + C2H2 -> A2R5C2H-C14H8 + H { A = 5.38E+07 n = 1.65 E = 10.71 }
2957
2958 # From A1 (x2/3)
2959 P49f: A2R5-C12H8 + C2H3 -> A2R5C2H2-C14H9 + H2 { A = 9.01E+16 n = -1.15 E = 61.01 }
2960
2961 # From A1-
2962 P50f: A2R5--C12H7 + C2H4 -> A2R5C2H2-C14H9 + H2 { A = 3.62E+28 n = -4.24 E = 99.85 }
2963
2964
2965 # From A1C2H2
2966 P51f: A2R5C2H2-C14H9 -> A2R5C2H-C14H8 + H { A = 2.09E+38 n = -7.74 E = 196.19 }
2967 P52f: A2R5C2H2-C14H9 + H -> A2R5C2H-C14H8 + H2 { A = 1.65E+11 n = 0.49 E = 44.48 }
2968 P53f: A2R5C2H2-C14H9 + OH-> A2R5C2H-C14H8 + H2O { A = 2.50E+12 n = .00 E = .00 }
2969
2970 # From A1 (x1/6)
2971 P54f: A2R5C2H-C14H8 -> A2R5C2H*-C14H7 + H { A = 2.15E+60 n =-12.48 E = 619.55 }
2972 P55f: A2R5C2H-C14H8 + H -> A2R5C2H*-C14H7 + H2 { A = 1.00E+08 n = 1.80 E = 68.42 }
2973 P56f: A2R5C2H-C14H8 + OH-> A2R5C2H*-C14H7 + H2O { A = 3.90E+03 n = 2.68 E = 3.07 }
2974
2975
2976 # Biphenyl
2977 # --------
2978
2979 # Park, Burova,, Rodgers & Lin 1999
2980 # Fitted exp rate
2981 P57f: A1-C6H6 + A1--C6H5 -> P2-C12H10 + H { A = 9.55E+11 n = .00 E = 9.07 }
2982
2983 # Tranter, Klippenstein, Harding, Giri, Yang, Keifer 2010
2984 P58f: A1--C6H5 + A1--C6H5 -> P2-C12H10 { A = 7.34E+20 n = -2.34 E = 17.26 }
2985 P59f: A1--C6H5 + A1--C6H5 -> P2--C12H9 + H { A = 2.44E+13 n = 0.89 E = 180.66 }
2986
2987 # From A1 (x2/3)
2988 P60f: P2-C12H10 -> P2--C12H9 + H { A = 8.60E+60 n =-12.48 E = 619.55 }
2989 P61f: P2-C12H10 + H -> P2--C12H9 + H2 { A = 4.01E+08 n = 1.80 E = 68.42 }
2990 P62f: P2-C12H10 + OH -> P2--C12H9 + H2O { A = 1.34E+04 n = 2.68 E = 3.07 }
2991
2992
2993 # Phenanthrene
2994 # ------------
2995
2996 # From A1C2H3*
2997 P63f: P2--C12H9 + C2H2 -> A3-C14H10 + H { A = 3.02E+03 n = 2.55 E = 13.31 }
2998
2999 # From P2 (x1/3)
3000 P64f: A1C2H-C8H6 + A1--C6H5 -> A3-C14H10 + H { A = 3.18E+11 n = .00 E = 9.07 }
3001 # From P2 & P2-
3002 P65f: A1C2H*-C8H5 + A1-C6H6 -> A3-C14H10 + H { A = 9.55E+11 n = .00 E = 9.07 }
3003 P66f: A1C2H*-C8H5 + A1--C6H5 -> A3-C14H10 { A = 1.39E+13 n = .00 E = 0.47 }
3004
3005
3006 # From A1 (x1/6)
3007 P67f: A2C2HA-C12H8 + C2H -> A3--C14H9 { A = 3.33E+13 n = .00 E = .00 }
3008 P68f: A2C2HB-C12H8 + C2H -> A3--C14H9 { A = 3.33E+13 n = .00 E = .00 }
3009
3010 # From A1C2H*
3011 P69f: A2C2HA*-C12H7 + C2H2 -> A3*-C14H9 { A = 1.34E+04 n = 2.50 E = 5.37 }
3012 P70f: A2C2HB*-C12H7 + C2H2 -> A3*-C14H9 { A = 1.34E+04 n = 2.50 E = 5.37 }
3013
3014 # From A1C2H2
3015 P71f: A2C2H2A-C12H9 + C2H2 -> A3-C14H10 + H { A = 2.62E+06 n = 2.00 E = 19.16 }
3016 P72f: A2C2H2B-C12H9 + C2H2 -> A3-C14H10 + H { A = 2.62E+06 n = 2.00 E = 19.16 }
3017
3018 # From A1 (x1/6)
3019 P73f: A2C2HA-C12H8 + C2H3 -> A3-C14H10 + H { A = 2.25E+16 n = -1.15 E = 61.01 }
3020 P74f: A2C2HB-C12H8 + C2H3 -> A3-C14H10 + H { A = 2.25E+16 n = -1.15 E = 61.01 }
3021
3022 # From A1-
3023 P75f: A2C2HA*-C12H7 + C2H4 -> A3-C14H10 + H { A = 3.62E+28 n = -4.24 E = 99.85 }
3024 P76f: A2C2HB*-C12H7 + C2H4 -> A3-C14H10 + H { A = 3.62E+28 n = -4.24 E = 99.85 }
3025
3026 # From A1-
3027 P77f: A2--C10H7 + C4H4 -> A3-C14H10 + H { A = 1.26E+04 n = 2.61 E = 6.00 }
3028 P78f: A2*-C10H7 + C4H4 -> A3-C14H10 + H { A = 1.26E+04 n = 2.61 E = 6.00 }
3029
3030
3031 # From A1 (x1/3)
3032 P79f: A3-C14H10 -> A3*-C14H9 + H { A = 4.30E+60 n =-12.48 E = 619.55 }
3033 P80f: A3-C14H10 + H -> A3*-C14H9 + H2 { A = 2.00E+08 n = 1.80 E = 68.42 }
3034 P81f: A3-C14H10 + OH -> A3*-C14H9 + H2O { A = 7.80E+03 n = 2.68 E = 3.07 }
3035
3036 # From A1 (x2/3)
3037 P82f: A3-C14H10 -> A3--C14H9 + H { A = 8.60E+60 n =-12.48 E = 619.55 }
3038 P83f: A3-C14H10 + H -> A3--C14H9 + H2 { A = 4.01E+08 n = 1.80 E = 68.42 }
3039 P84f: A3-C14H10 + OH -> A3--C14H9 + H2O { A = 1.56E+04 n = 2.68 E = 3.07 }
3040
3041 # Frenklach 2005
3042 P85f: A3*-C14H9 -> A2R5--C12H7 + C2H2 { A = 1.30E+11 n = 1.08 E = 294.55 }
3043
3044
3045 # Acephenanthrylene
3046 # -----------------
3047
3048 # From A1C2H*
3049 P86f: A2R5C2H*-C14H7 + C2H2 -> A3R5--C16H9 { A = 1.34E+04 n = 2.50 E = 5.37 }
3050
3051 # From A1C2H2
3052 P87f: A2R5C2H2-C14H9 + C2H2 -> A3R5-C16H10 + H { A = 2.62E+06 n = 2.00 E = 19.16 }
3053
3054 # From A2-
3055 P88f: A3--C14H9 + C2H2 -> A3R5-C16H10 + H { A = 2.81E+07 n = 1.77 E = 9.37 }
3056
3057 # From A1-
3058 P89f: A2R5--C12H7 + C4H4 -> A3R5-C16H10 + H { A = 1.26E+04 n = 2.61 E = 6.00 }
3059
3060
3061 # From A1 (x1/3)
3062 P90f: A3R5-C16H10 -> A3R5--C16H9 + H { A = 2.15E+60 n =-12.48 E = 619.55 }
3063 P91f: A3R5-C16H10 + H -> A3R5--C16H9 + H2 { A = 2.01E+08 n = 1.80 E = 68.42 }
3064 P92f: A3R5-C16H10 + OH -> A3R5--C16H9 + H2O { A = 7.80E+03 n = 2.68 E = 3.07 }
3065
3066
3067 # Pyrene
3068 # ------
3069
3070 # From A2*
3071 P93f: A3*-C14H9 + C2H2 -> A4-C16H10 + H { A = 5.38E+07 n = 1.65 E = 10.71 }
3072
3073 # From A1 (x4/3)
3074 P94f: A4-C16H10 -> A4--C16H9 + H { A = 1.72E+60 n =-12.48 E = 619.55 }
3075 P95f: A4-C16H10 + H -> A4--C16H9 + H2 { A = 8.03E+08 n = 1.80 E = 68.42 }
3076 P96f: A4-C16H10 + OH -> A4--C16H9 + H2O { A = 3.12E+04 n = 2.68 E = 3.07 }
3077
3078
3079 # Cyclopenta[cd]pyrene
3080 # --------------------
3081
3082 # From A2-/A2*
3083 P97f: A4--C16H9 + C2H2 -> A4R5-C18H10 + H { A = 2.81E+07 n = 1.77 E = 9.37 }
3084 P98f: A3R5--C16H9 + C2H2 -> A4R5-C18H10 + H { A = 5.38E+07 n = 1.65 E = 10.71 }
3085
3086
3087 # Fluoranthene
3088 # ------------
3089
3090 # From A1+A1- (x2/3 and x1)
3091 P99 : A2-C10H8 + A1--C6H5 -> FLTN-C16H10 + H2+H { A = 6.37E+11 n = .00 E = 9.07 }
3092 P100: A2--C10H7 + A1-C6H6 -> FLTN-C16H10 + H2+H { A = 9.55E+11 n = .00 E = 9.07 }
3093
3094 # From A1-+A1-
3095 P101: A2--C10H7 + A1--C6H5 -> FLTN-C16H10 + 2H { A = 1.39E+13 n = .00 E = 0.47 }
3096
3097
3098
3099 #==========================================================================#
3100 # #
3101 # Higher PAH Oxidation Chemistry #
3102 # Adapted from Benzene #
3103 # #
3104 #==========================================================================#
3105
3106 # From A1-+O2
3107 OX01 : A3*-C14H9 + O2 -> A2C2H2B-C12H9 + 2CO { A = 8.57E+20 n = -2.27 E = 30.08 }
3108 OX02 : A3--C14H9 + O2 -> A2C2H2A-C12H9 + 2CO { A = 8.57E+20 n = -2.27 E = 30.08 }
3109 OX03 : A4--C16H9 + O2 -> A3*-C14H9 + 2CO { A = 8.57E+20 n = -2.27 E = 30.08 }
3110 OX04 : A2R5--C12H7 + O2 -> A2--C10H7 + 2CO { A = 8.57E+20 n = -2.27 E = 30.08 }
3111 OX05 : A3R5--C16H9 + O2 -> A3*-C14H9 + 2CO { A = 8.57E+20 n = -2.27 E = 30.08 }
3112
3113 # From A1+OH
3114 # Rescaled by number of active sites
3115 OX06 : A3-C14H10 + OH -> A2C2HA-C12H8 +CH3+CO { A = 1.10E+02 n = 3.25 E = 23.39 }
3116 OX07 : A3-C14H10 + OH -> A2C2HB-C12H8 +CH3+CO { A = 1.10E+02 n = 3.25 E = 23.39 }
3117 OX08 : A4-C16H10 + OH -> A3-C14H10 + HCCO { A = 2.20E+02 n = 3.25 E = 23.39 }
3118 OX09 : A2R5-C12H8 + OH -> A2-C10H8 + HCCO { A = 1.76E+02 n = 3.25 E = 23.39 }
3119 OX10 : A3R5-C16H10 + OH -> A3-C14H10 + HCCO { A = 2.20E+02 n = 3.25 E = 23.39 }
3120 OX11 : A4R5-C18H10 + OH -> A4-C16H10 + HCCO { A = 2.20E+02 n = 3.25 E = 23.39 }
3121 OX12 : FLTN-C16H10 + OH -> A3-C14H10 + HCCO { A = 2.20E+02 n = 3.25 E = 23.39 }
3122
3123
3124
3125 #================================================================#
3126 # #
3127 # Soot Formation #
3128 # #
3129 #================================================================#
3130
3131 ###### H-Abstraction ######
3132
3133 # Tokmakov & Lin 1999/2002
3134 # Rates indep of pressure
3135 # 1/6 of forward and full backward
3136 SOOT1f: Soot-CH + OH -> Soot-C + H2O { A = 6.72E+01 n = 3.33 E = 6.09 }
3137 SOOT1b: Soot-C + H2O -> Soot-CH + OH { A = 6.44E-01 n = 3.79 E = 27.96 }
3138
3139 # Mebel & Lin 1997
3140 # Rates indep of pressure
3141 # 1/6 of forward and full backward
3142 SOOT2f: Soot-CH + H -> Soot-C + H2 { A = 1.00E+08 n = 1.80 E = 68.42 }
3143 SOOT2b: Soot-C + H2 -> Soot-CH + H { A = 8.68E+04 n = 2.36 E = 25.46 }
3144
3145 # Harding, Georgievskii & Klippenstein 2005
3146 # High Pressure Limit
3147 # 1/6 of forward and full backward
3148 SOOT3f: Soot-CH -> Soot-C + H { A = 1.13E+16 n = -0.06 E = 476.05 }
3149 SOOT3b: Soot-C + H -> Soot-CH { A = 4.17E+13 n = 0.15 E = .00 }
3150
3151
3152 ###### C2H2-Addition ######
3153
3154 # Tokmakov & Lin 2004
3155 # High pressure rates for A1- + C2H2 <=> A1C2H2 (x2)
3156 SOOT4: Soot-C + C2H2 -> Soot-CH noCheck { A = 2.52E+09 n = 1.10 E = 17.13 }
3157
3158
3159 ###### Oxidation ######
3160
3161 # Assume first reaction step is the limiting step:
3162 # Attack by O2 or OH
3163
3164 # Kazakov, Wang & Frenklach 1995
3165 SOOT5: Soot-C + O2 -> Soot-C + 2CO noCheck { A = 2.20E+12 n = .00 E = 31.38 }
3166
3167 # Sarofim 1981
3168 # Directly Coded in FlameMaster
3169 # From collision efficiency - 0.13
3170 SOOT6 : Soot-CH + OH -> Soot-C + CO noCheck { A = 0.00E+00 n = .00 E = .00 }
3171
3172
3173 # **** Third Body *****
3174
3175 Let M0 = 1.0 [OTHER].
3176
3177 Let M1 = 0.0 [H2] + 0.0 [H2O] + 0.63 [AR] + 0.00 [CO2] + 1.0 [OTHER].
3178 Let M2 = 2.5 [H2] + 12.0 [H2O] + 0.75 [AR] + 1.0 [OTHER].
3179 Let M3 = 2.5 [H2] + 12.0 [H2O] + 0.00 [AR] + 1.0 [OTHER].
3180 Let M4 = 1.5 [H2] + 11.7 [H2O] + 0.52 [AR] + 1.09 [CO] + 2.18 [CO2] + 0.89 [O2] + 1.0 [OTHER].
3181 Let M5 = 3.0 [H2] + 0.0 [H2O] + 2.00 [N2] + 1.50 [O2] + 1.0 [OTHER].
3182 Let M6 = 2.5 [H2] + 9.0 [H2O] + 1.50 [N2] + 1.0 [OTHER].
3183
3184 Let M7 = 2.0 [H2] + 12.0 [H2O] + 0.70 [AR] + 1.75 [CO] + 3.60 [CO2] + 1.0 [OTHER].
3185 Let M8 = 2.0 [H2] + 0.0 [H2O] + 1.75 [CO] + 3.60 [CO2] + 1.0 [OTHER].
3186
3187 Let M9 = 2.0 [H2] + 6.0 [H2O] + 0.70 [AR] + 1.50 [CO] + 2.00 [CO2] + 2 [CH4] + 3 [C2H6] + 1.0 [OTHER].
3188
3189 Let M10= 2.5 [H2] + 16.3 [H2O] + 0.88 [AR] + 1.0 [OTHER].
3190
3191 Let M11= 2.0 [H2] + 6.0 [H2O] + 0.85 [AR] + 1.50 [CO] + 2.00 [CO2] + 2 [CH4] + 1.0 [OTHER].
3192

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