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Revision 2.1 - (hide annotations) (download)
Mon Sep 15 23:59:06 2014 UTC (9 years, 7 months ago) by gblanqu
Branch: MAIN
Changes since 2.0: +5 -5 lines 
Addition of low T in Chemkin version.
Fix name of N-C5H11 for low T.
Newer rate for C2H4 decomposition.
1 gblanqu 2.0 Let allowed atoms be C, H, O, N, AR.
2     Let additional species be N2.
3     Let temperature exponent be n_k.
4     Let order of reaction be n.
5     Let units for A be [ cm^(3(n-1)) / ( s * mole^(n-1) * K^n_k ) ].
6     Let units for E be [ kJ / mole ].
7     Let symbol for soot be SOOT.
8    
9    
10     #=========================================================================#
11     # #
12     # "An Improved H2/O2 Mechanism #
13     # based on Recent Shock Tube/Laser Absorption Measurements" #
14     # Hong, Davidson, Hanson, Combust. Flame (2011) #
15     # #
16     #=========================================================================#
17    
18    
19     # Hydrogen/oxygen
20     # ---------------
21    
22     1f: H + O2 -> O + OH { A = 1.04E+14 n = .00 E = 63.96 }
23     2f: O + H2 -> H + OH { A = 3.82E+12 n = .00 E = 33.25 }
24     3f: O + H2 -> H + OH { A = 8.79E+14 n = .00 E = 80.21 }
25     4f: OH + H2 -> H + H2O { A = 2.17E+08 n = 1.52 E = 14.46 }
26     5f: OH + OH -> O + H2O { A = 3.57E+04 n = 2.40 E = -8.83 }
27    
28     # Davis et al. 2005
29     6f: 2 H + M1 -> H2 + M1 { A = 1.78E+18 n = -1.00 E = .00 }
30     7f: 2 H + H2 -> H2 + H2 { A = 9.00E+16 n = -0.60 E = .00 }
31     8f: 2 H + H2O -> H2 + H2O { A = 5.62E+19 n = -1.25 E = .00 }
32     9f: 2 H + CO2 -> H2 + CO2 { A = 5.50E+20 n = -2.00 E = .00 }
33    
34     10f: O + H + M2 -> OH + M2 { A = 4.71E+18 n = -1.00 E = .00 }
35     11f: O + O + M3 -> O2 + M3 { A = 6.16E+15 n = -0.50 E = .00 }
36     12f: O + O + AR -> O2 + AR { A = 1.89E+13 n = .00 E = -7.48 }
37    
38     # All rates recombined into a single
39     # Similar to Davis et al. 2005
40     # Collider efficiency evaluated at 1200K
41     13f: H + O2 + M4 -> HO2 + M4 { Ai= 5.59E+13 ni= 0.20 Ei= .00
42     A = 2.65E+19 n = -1.30 E = .00
43     fca = 0.3 fcta = 1.0E-10
44     fcb = 0.7 fctb = 1.0E+10
45     fcc = 1.0 fctc = 1.0E+10 }
46    
47     14f: H2O + M5 -> OH + H + M5 { A = 6.06E+27 n = -3.31 E = 505.30 }
48     15f: H2O + H2O -> OH + H + H2O { A = 1.00E+26 n = -2.44 E = 502.75 }
49    
50    
51     # Hydroperoxy radical
52     # -------------------
53    
54     16f: HO2 + H -> H2 + O2 { A = 3.66E+06 n = 2.09 E = -6.07 }
55     17f: HO2 + H -> O + H2O { A = 1.45E+12 n = .00 E = .00 }
56     18f: HO2 + H -> OH + OH { A = 7.08E+13 n = .00 E = 1.26 }
57     19f: HO2 + O -> OH + O2 { A = 1.63E+13 n = .00 E = -1.86 }
58    
59     20f: HO2 + OH -> H2O + O2 { A = 2.89E+13 n = .00 E = -2.09 }
60     21f: HO2 + HO2 -> H2O2 + O2 { A = 1.30E+11 n = .00 E = -6.71 }
61     22f: HO2 + HO2 -> H2O2 + O2 { A = 4.20E+14 n = .00 E = 50.12 }
62    
63    
64     # Hydrogen peroxide
65     # -----------------
66    
67     # Low P from Hong et al. 2011 - refitted
68     # Rest from Davis et al. 2005
69     23f: 2 OH + M6 -> H2O2 + M6 { A = 2.73E+19 n = -1.50 E = -9.59
70     Ai= 1.11E+14 ni= -0.37 Ei= .00
71     fcA = 0.2654 fctA = 94
72     fcb = 0.7346 fctb = 1756
73     fcc = 1.0 fctc = 5182 }
74    
75     24f: H2O2 + H -> H2O + OH { A = 1.02E+13 n = .00 E = 14.97 }
76     25f: H2O2 + H -> HO2 + H2 { A = 1.21E+07 n = 2.00 E = 21.76 }
77     26f: H2O2 + O -> HO2 + OH { A = 8.43E+11 n = .00 E = 16.61 }
78     27f: H2O2 + OH -> HO2 + H2O { A = 1.74E+12 n = .00 E = 1.33 }
79     28f: H2O2 + OH -> HO2 + H2O { A = 7.59E+13 n = .00 E = 29.77 }
80    
81    
82    
83     #=========================================================================#
84     # #
85     # "An optimized kinetic model of H2/CO combustion" #
86     # Davis, Joshi, Wang, and Egolfopoulos #
87     # Proc. Comb. Inst. 30 (2005) 1283-1292 #
88     # #
89     #=========================================================================#
90    
91    
92     # Carbon oxides
93     # -------------
94    
95     30f: CO + O + M7 -> CO2 + M7 { A = 1.17E+24 n = -2.79 E = 17.54
96     Ai= 1.36E+10 ni= .00 Ei= 9.97
97     fcc = 1.0 fctc = 0.0 }
98     31f: CO + OH -> CO2 + H { A = 8.00E+11 n = 0.14 E = 30.76 }
99     32f: CO + OH -> CO2 + H { A = 8.78E+10 n = 0.03 E = -0.07 }
100     33f: CO + O2 -> CO2 + O { A = 1.12E+12 n = .00 E = 199.58 }
101     34f: CO + HO2 -> CO2 + OH { A = 3.01E+13 n = .00 E = 96.23 }
102    
103     35f: HCO + M8 -> CO + H + M8 { A = 1.87E+17 n = -1.00 E = 71.13 }
104     36f: HCO + H2O -> CO + H + H2O { A = 2.24E+18 n = -1.00 E = 71.13 }
105    
106     37f: HCO + H -> CO + H2 { A = 1.20E+14 n = .00 E = .00 }
107     38f: HCO + O -> CO + OH { A = 3.00E+13 n = .00 E = .00 }
108     39f: HCO + OH -> CO + H2O { A = 3.02E+13 n = .00 E = .00 }
109    
110     40f: HCO + O -> CO2 + H { A = 3.00E+13 n = .00 E = .00 }
111    
112     # New fit to experimental data
113     # Colbergs & Friedrichs 2006
114     41f: HCO + O2 -> CO + HO2 { A = 5.31E+10 n = 0.69 E = -0.52 }
115    
116    
117    
118     #=========================================================================#
119     # #
120     # Chemistry of excited OH and CH states #
121     # de Vries, Hall, Simmons, Rickard, Kalitan, Petersen 2007 #
122     # (simplified) #
123     # #
124     #=========================================================================#
125    
126    
127     # Excited OH*
128     # -----------
129    
130     E01f: S-OH -> OH { A = 1.40E+06 n = .00 E = .00 }
131     E02f: S-OH + M0 -> OH + M0 { A = 2.17E+10 n = 0.50 E = 8.62 }
132     E03f: S-OH + O2 -> OH + O2 { A = 2.10E+12 n = 0.50 E = -2.02 }
133    
134     E04f: O + H + M0 -> S-OH + M0 { A = 3.10E+14 n = .00 E = 41.84 }
135     E05f: CH + O2 -> S-OH + CO { A = 3.24E+14 n = -0.40 E = 17.36 }
136    
137    
138     # Excited CH*
139     # -----------
140    
141     E06f: S-CH -> CH { A = 1.86E+06 n = .00 E = .00 }
142     E07f: S-CH + M0 -> CH + M0 { A = 4.00E+10 n = 0.50 E = .00 }
143     E08f: S-CH + O2 -> CH + O2 { A = 2.48E+06 n = 2.14 E = -7.20 }
144    
145     E09f: C + H + M0 -> S-CH + M0 { A = 3.63E+13 n = .00 E = .00 }
146     E10f: C2H + O -> S-CH + CO { A = 5.20E+11 n = .00 E = 10.88 }
147    
148     # Elsamra, Vranckx, Carl 2005
149     E11f: C2H + O2 -> S-CH + CO2 { A = 6.02E-04 n = 4.40 E = -9.56 }
150    
151    
152    
153     #=========================================================================#
154     # #
155     # GRI-MECH version 3.0 #
156     # http://www.me.berkeley.edu/gri_mech/ #
157     # #
158     # Gregory P. Smith, David M. Golden, Michael Frenklach, Nigel W. Moriarty #
159     # Boris Eiteneer, Mikhail Goldenberg, C. Thomas Bowman, Ronald K. Hanson, #
160     # Soonho Song, William C. Gardiner, Jr., Vitali V. Lissianski, Zhiwei Qin #
161     # #
162     #=========================================================================#
163    
164     # Carbon
165     # ------
166    
167     G01f: C + OH -> CO + H { A = 5.00E+13 n = .00 E = .00 }
168     G02f: C + O2 -> CO + O { A = 5.80E+13 n = .00 E = 2.41 }
169    
170    
171     # Methylidyne
172     # -----------
173    
174     # Back to value before GRI opt
175     # Dean, Davidson, Hanson 1991
176     G03f: CH + H -> C + H2 { A = 1.10E+14 n = .00 E = .00 }
177    
178     G04f: CH + O -> CO + H { A = 5.70E+13 n = .00 E = .00 }
179     G05f: CH + OH -> HCO + H { A = 3.00E+13 n = .00 E = .00 }
180     G06f: CH + H2 -> T-CH2 + H { A = 1.08E+14 n = .00 E = 13.01 }
181     G07f: CH + H2 + M9 -> CH3 + M9 { A = 4.82E+25 n = -2.80 E = 2.47
182     Ai= 1.97E+12 ni= 0.43 Ei= -1.55
183     fcA = 0.422 fctA = 122
184     fcb = 0.578 fctb = 2535
185     fcc = 1.0 fctc = 9365 }
186     G08f: CH + H2O -> CH2O + H { A = 5.71E+12 n = .00 E = -3.16 }
187     G09f: CH + O2 -> HCO + O { A = 6.71E+13 n = .00 E = .00 }
188     G10f: CH + CO + M9 -> HCCO + M9 { A = 2.69E+28 n = -3.74 E = 8.10
189     Ai= 5.00E+13 ni= .00 Ei= .00
190     fcA = 0.4243 fctA = 237
191     fcb = 0.5757 fctb = 1652
192     fcc = 1.0 fctc = 5069 }
193     G11f: CH + CO2 -> HCO + CO { A = 1.90E+14 n = .00 E = 66.07 }
194    
195    
196     # Carbon oxides
197     # -------------
198    
199     G12f: CO + H2 + M9 -> CH2O + M9 { A = 5.07E+27 n = -3.42 E = 352.92
200     Ai= 4.30E+07 ni= 1.50 Ei= 333.05
201     fcA = 0.068 fctA = 197
202     fcb = 0.932 fctb = 1540
203     fcc = 1.0 fctc = 10300 }
204     G13f: HCO + H + M9 -> CH2O + M9 { A = 2.47E+24 n = -2.57 E = 1.78
205     Ai= 1.09E+12 ni= .48 Ei= -1.09
206     fcA = 0.2176 fctA = 271
207     fcb = 0.7824 fctb = 2755
208     fcc = 1.0 fctc = 6570 }
209    
210    
211     # Methylene (triplet)
212     # -------------------
213    
214     G14f: T-CH2 + H + M9 -> CH3 + M9 { A = 1.04E+26 n = -2.76 E = 6.69
215     Ai= 6.00E+14 ni= .00 Ei= .00
216     fcA = 0.438 fctA = 91
217     fcb = 0.562 fctb = 5836
218     fcc = 1.0 fctc = 8552 }
219     G15f: T-CH2 + O -> HCO + H { A = 8.00E+13 n = .00 E = .00 }
220     G16f: T-CH2 + OH -> CH2O + H { A = 2.00E+13 n = .00 E = .00 }
221     G17f: T-CH2 + OH -> CH + H2O { A = 1.13E+07 n = 2.00 E = 12.55 }
222     G18f: T-CH2 + H2 -> CH3 + H { A = 5.00E+05 n = 2.00 E = 30.25 }
223    
224     # Alvarez, Moore, 1994
225     # Lee, Matsui, Chen, Wang 2012
226     # (revised branching ratios 0.58/0.20/0.22)
227     G19f: T-CH2 + O2 -> HCO + OH { A = 9.57E+12 n = .00 E = 7.27 }
228     G20f: T-CH2 + O2 -> CH2O + O { A = 3.30E+12 n = .00 E = 7.27 }
229     G21f: T-CH2 + O2 -> CO2 + H2 { A = 3.63E+12 n = .00 E = 7.27 }
230    
231     G22f: T-CH2 + HO2 -> CH2O + OH { A = 2.00E+13 n = .00 E = .00 }
232     G23f: T-CH2 + C -> C2H + H { A = 5.00E+13 n = .00 E = .00 }
233     G24f: T-CH2 + CO + M9 -> CH2CO + M9 { A = 2.69E+33 n = -5.11 E = 29.69
234     Ai= 8.10E+11 ni= .50 Ei= 18.87
235     fcA = 0.4093 fctA = 275
236     fcb = 0.5907 fctb = 1226
237     fcc = 1.0 fctc = 5185 }
238     G25f: T-CH2 + CH -> C2H2 + H { A = 4.00E+13 n = .00 E = .00 }
239     G26f: T-CH2 + T-CH2 -> C2H2 + H2 { A = 1.60E+15 n = .00 E = 49.97 }
240     G27 : T-CH2 + T-CH2 -> C2H2 + 2 H { A = 2.00E+14 n = .00 E = 45.98 }
241    
242    
243     # Methylene (singlet)
244     # -------------------
245    
246     G28f: S-CH2 + N2 -> T-CH2 + N2 { A = 1.50E+13 n = .00 E = 2.51 }
247     G29f: S-CH2 + AR -> T-CH2 + AR { A = 9.00E+12 n = .00 E = 2.51 }
248     G30f: S-CH2 + CO -> T-CH2 + CO { A = 9.00E+12 n = .00 E = .00 }
249     G31f: S-CH2 + CO2 -> T-CH2 + CO2 { A = 7.00E+12 n = .00 E = .00 }
250     G32f: S-CH2 + H2O -> T-CH2 + H2O { A = 3.00E+13 n = .00 E = .00 }
251    
252     G33f: S-CH2 + H -> CH + H2 { A = 3.00E+13 n = .00 E = .00 }
253     G34f: S-CH2 + O -> CO + H2 { A = 1.50E+13 n = .00 E = .00 }
254     G35f: S-CH2 + O -> HCO + H { A = 1.50E+13 n = .00 E = .00 }
255     G36f: S-CH2 + H2 -> CH3 + H { A = 7.00E+13 n = .00 E = .00 }
256     G37 : S-CH2 + O2 -> CO + OH + H { A = 2.80E+13 n = .00 E = .00 }
257     G38f: S-CH2 + O2 -> CO + H2O { A = 1.20E+13 n = .00 E = .00 }
258     G39f: S-CH2 + H2O + M9 -> CH3OH + M9 { A = 1.88E+38 n = -6.36 E = 21.09
259     Ai= 4.82E+17 ni= -1.16 Ei= 4.79
260     fcA = 0.3973 fctA = 208
261     fcb = 0.6027 fctb = 3922
262     fcc = 1.0 fctc = 10180 }
263    
264     G40f: S-CH2 + OH -> CH2O + H { A = 3.00E+13 n = .00 E = .00 }
265     G41 : S-CH2 + H2O -> CH2O + H2 { A = 6.82E+10 n = .25 E = -3.91 }
266     G42f: S-CH2 + CO2 -> CH2O + CO { A = 1.40E+13 n = .00 E = .00 }
267    
268    
269     # Formaldehyde
270     # ------------
271    
272     # Dames & Golden 2013
273     G43f: CH2OH + M9 -> CH2O + H + M9 { A = 3.50E+21 n = -1.99 E = 100.41
274     Ai= 7.37E+10 ni= 0.81 Ei= 165.61
275     fcA = 0.156 fctA = 900
276     fcb = 0.844 fctb = 1
277     fcc = 1.0 fctc = 3315 }
278     G44f: CH3O + M9 -> CH2O + H + M9 { A = 6.02E+16 n = -0.55 E = 75.41
279     Ai= 1.13E+10 ni= 1.21 Ei= 100.77
280     fcA = 0.659 fctA = 28
281     fcb = 0.341 fctb = 1000
282     fcc = 1.0 fctc = 2339 }
283    
284     G45f: CH2O + H -> HCO + H2 { A = 5.74E+07 n = 1.90 E = 11.47 }
285     G46f: CH2O + O -> HCO + OH { A = 3.90E+13 n = .00 E = 14.81 }
286     G47f: CH2O + OH -> HCO + H2O { A = 3.43E+09 n = 1.18 E = -1.87 }
287     G48f: CH2O + O2 -> HCO + HO2 { A = 1.00E+14 n = .00 E = 167.36 }
288     G49f: CH2O + HO2 -> HCO + H2O2 { A = 5.60E+06 n = 2.00 E = 50.21 }
289    
290     G50f: CH2O + CH -> CH2CO + H { A = 9.46E+13 n = .00 E = -2.16 }
291    
292    
293     # Methyl radical
294     # --------------
295    
296     # Golden 2013
297     # Baulch et al.; Troe Ushakov
298     G51f: CH3 + H + M9 -> CH4 + M9 { A = 2.79E+34 n = -5.10 E = 11.65
299     Ai= 4.36E+13 ni= 0.19 Ei= .00
300     fcA = 0.37 fctA = 61
301     fcb = 0.63 fctb = 3315
302     fcc = 1.0 fctc = 1e10 }
303    
304     # Harding, Klippenstein, Georgievskii 2005
305     # Reactions lumped - Products changed
306     G52f: CH3 + O -> CH2O + H { A = 5.54E+13 n = 0.05 E = -0.57 }
307    
308     G54f: CH3 + OH + M9 -> CH3OH + M9 { A = 4.00E+36 n = -5.92 E = 13.14
309     Ai= 2.79E+18 ni= -1.43 Ei= 5.57
310     fcA = 0.588 fctA = 195
311     fcb = 0.412 fctb = 5900
312     fcc = 1.0 fctc = 6394 }
313     G55f: CH3 + OH -> T-CH2 + H2O { A = 5.60E+07 n = 1.60 E = 22.68 }
314     G56f: CH3 + OH -> S-CH2 + H2O { A = 6.44E+17 n = -1.34 E = 5.93 }
315     G57: CH3 + OH -> CH2O + H2 { A = 8.00E+09 n = .00 E = -7.34 }
316    
317     # Petersen et al. 2007
318     G58f: CH3 + O2 -> CH3O + O { A = 1.38E+13 n = .00 E = 127.70 }
319     G59f: CH3 + O2 -> CH2O + OH { A = 5.87E+11 n = .00 E = 57.91 }
320     G60f: CH3 + O2 + M0 -> CH3O2 + M0 { A = 3.82E+31 n = -4.89 E = 14.36
321     Ai= 1.01E+08 ni= 1.63 Ei= .00
322     fca = 0.955 fcta = 880.1
323     fcb = 0.045 fctb = 2.5E+9
324     fcc = 1 fctc = 1.786E+09 }
325     G61f: CH3O2 + CH3 -> CH3O + CH3O { A = 1.00E+13 n = .00 E = -5.02 }
326     G62 : CH3O2 + CH3O2 -> CH3O + CH3O + O2 { A = 1.40E+16 n = -1.61 E = 7.78 }
327     G63 : CH3O2 + HO2 -> CH3O + OH + O2 { A = 2.47E+11 n = .00 E = -6.57 }
328     G64 : CH3O2 + CH2O -> CH3O + OH + HCO { A = 1.99E+12 n = .00 E = 48.83 }
329    
330     # Jasper, Klippensteion, Harding 2009
331     G65f: CH3 + HO2 -> CH3O + OH { A = 1.00E+12 n = 0.29 E = -2.87 }
332     G66f: CH3 + HO2 -> CH4 + O2 { A = 1.19E+05 n = 2.23 E = -12.65 }
333    
334     G67f: CH3 + H2O2 -> CH4 + HO2 { A = 2.45E+04 n = 2.47 E = 21.67 }
335     G68f: CH3 + HCO -> CH4 + CO { A = 2.65E+13 n = .00 E = .00 }
336     G69f: CH3 + CH2O -> CH4 + HCO { A = 3.32E+03 n = 2.81 E = 24.52 }
337    
338     G70f: CH3 + C -> C2H2 + H { A = 5.00E+13 n = .00 E = .00 }
339     G71f: CH3 + CH -> C2H3 + H { A = 3.00E+13 n = .00 E = .00 }
340     G72f: CH3 + T-CH2 -> C2H4 + H { A = 1.00E+14 n = .00 E = .00 }
341     G73f: CH3 + S-CH2 -> C2H4 + H { A = 1.20E+13 n = .00 E = -2.39 }
342     G74f: CH3 + CH3 -> C2H5 + H { A = 6.84E+12 n = 0.10 E = 44.35 }
343    
344    
345     # Methoxy radical
346     # ---------------
347    
348     G75f: CH3O + H + M9 -> CH3OH + M9 { A = 4.66E+41 n = -7.44 E = 58.91
349     Ai= 2.43E+12 ni= .52 Ei= 0.21
350     fcA = 0.30 fctA = 100
351     fcb = 0.70 fctb = 90000
352     fcc = 1.0 fctc = 10000 }
353     G76f: CH3O + H -> CH3 + OH { A = 1.50E+12 n = 0.50 E = -0.46 }
354     G77f: CH3O + H -> S-CH2 + H2O { A = 2.62E+14 n = -0.23 E = 4.48 }
355    
356     G78f: CH3O + H -> CH2O + H2 { A = 2.00E+13 n = .00 E = .00 }
357     G79f: CH3O + O -> CH2O + OH { A = 1.00E+13 n = .00 E = .00 }
358     G80f: CH3O + OH -> CH2O + H2O { A = 5.00E+12 n = .00 E = .00 }
359    
360     # Baulch et al. 2005
361     G81f: CH3O + O2 -> CH2O + HO2 { A = 6.17E+10 n = .00 E = 7.32 }
362    
363     G82f: CH2OH + H + M9 -> CH3OH + M9 { A = 4.36E+31 n = -4.65 E = 21.26
364     Ai= 1.06E+12 ni= 0.50 Ei= 0.36
365     fcA = 0.400 fctA = 100
366     fcb = 0.600 fctb = 9000
367     fcc = 1.0 fctc = 10000 }
368     G83f: CH2OH + H -> CH3 + OH { A = 1.65E+11 n = 0.65 E = -1.19 }
369     G84f: CH2OH + H -> S-CH2 + H2O { A = 3.28E+13 n = -0.09 E = 2.55 }
370    
371     G85f: CH2OH + H -> CH2O + H2 { A = 2.00E+13 n = .00 E = .00 }
372     G86f: CH2OH + O -> CH2O + OH { A = 1.00E+13 n = .00 E = .00 }
373     G87f: CH2OH + OH -> CH2O + H2O { A = 5.00E+12 n = .00 E = .00 }
374     G88f: CH2OH + O2 -> CH2O + HO2 { A = 1.80E+13 n = .00 E = 3.77 }
375    
376     G89f: CH3O + H -> CH2OH + H { A = 4.15E+07 n = 1.63 E = 8.05 }
377    
378    
379     # Methane
380     # -------
381    
382     G90f: CH4 + H -> CH3 + H2 { A = 6.60E+08 n = 1.62 E = 45.36 }
383     G91f: CH4 + O -> CH3 + OH { A = 1.02E+09 n = 1.50 E = 35.98 }
384     G92f: CH4 + OH -> CH3 + H2O { A = 1.00E+08 n = 1.60 E = 13.05 }
385     G94f: CH4 + T-CH2 -> CH3 + CH3 { A = 2.46E+06 n = 2.00 E = 34.60 }
386     G95f: CH4 + S-CH2 -> CH3 + CH3 { A = 1.60E+13 n = .00 E = -2.39 }
387    
388     G93f: CH4 + CH -> C2H4 + H { A = 6.00E+13 n = .00 E = .00 }
389    
390    
391     # Methanol
392     # --------
393    
394     G96f: CH3OH + H -> CH2OH + H2 { A = 1.70E+07 n = 2.10 E = 20.38 }
395     G97f: CH3OH + O -> CH2OH + OH { A = 3.88E+05 n = 2.50 E = 12.97 }
396     G98f: CH3OH + OH -> CH2OH + H2O { A = 1.44E+06 n = 2.00 E = -3.52 }
397     G99f: CH3OH + CH3 -> CH2OH + CH4 { A = 3.00E+07 n = 1.50 E = 41.59 }
398    
399     G100f: CH3OH + H -> CH3O + H2 { A = 4.20E+06 n = 2.10 E = 20.38 }
400     G101f: CH3OH + O -> CH3O + OH { A = 1.30E+05 n = 2.50 E = 20.92 }
401     G102f: CH3OH + OH -> CH3O + H2O { A = 6.30E+06 n = 2.00 E = 6.28 }
402     G103f: CH3OH + CH3 -> CH3O + CH4 { A = 1.00E+07 n = 1.50 E = 41.59 }
403    
404    
405     # Acetyl radical
406     # --------------
407    
408     G104f: C2H + H + M9 -> C2H2 + M9 { A = 2.60E+33 n = -4.80 E = 7.95
409     Ai= 1.00E+17 ni= -1.00 Ei= .00
410     fcA = 0.3536 fctA = 132
411     fcb = 0.6464 fctb = 1315
412     fcc = 1.0 fctc = 5566 }
413     G105f: C2H + O -> CH + CO { A = 5.00E+13 n = .00 E = .00 }
414     G106f: C2H + OH -> HCCO + H { A = 2.00E+13 n = .00 E = .00 }
415     G107f: C2H + O2 -> HCO + CO { A = 1.00E+13 n = .00 E = -3.16 }
416    
417     # Carl, Vereecken & Peeters 2007
418     G108f: C2H + H2 -> C2H2 + H { A = 2.36E+05 n = 2.57 E = 1.08 }
419    
420    
421     # Ketenyl radical
422     # ---------------
423     # Revised based on Carl, Vereecken & Peeters 2007
424    
425     G109f: HCCO + H -> S-CH2 + CO { A = 1.00E+14 n = .00 E = .00 }
426     G110f: HCCO + CH -> C2H2 + CO { A = 5.00E+13 n = .00 E = .00 }
427     G111f: HCCO + T-CH2 -> C2H3 + CO { A = 3.00E+13 n = .00 E = .00 }
428     G112f: HCCO + CH3 -> C2H4 + CO { A = 5.00E+13 n = .00 E = .00 }
429     G113 : HCCO + HCCO -> C2H2 + 2 CO { A = 1.00E+13 n = .00 E = .00 }
430    
431     G114 : HCCO + O -> H + 2 CO { A = 7.22E+13 n = .00 E = .00 }
432    
433     # Mai, Raghunath, Le, Huynh, Nam, Lin 2014
434     G115f: HCCO + OH -> CH2O + CO { A = 1.88E+16 n = -0.59 E = 0.61 }
435     G116f: HCCO + OH -> T-CH2 + CO2 { A = 8.97E+04 n = 2.09 E = -9.19 }
436    
437     # Klippenstein, Miller, Harding 2002
438     G117 : HCCO + O2 -> CO2 + CO + H { A = 4.78E+12 n = -0.14 E = 4.81 }
439     G118 : HCCO + O2 -> 2CO + OH { A = 1.91E+11 n = -0.02 E = 4.28 }
440    
441    
442     # Acetylene
443     # ---------
444    
445     # Miller & Klippenstein 2004
446     # Refitted TROE form
447     G119f: C2H2 + H + M9 -> C2H3 + M9 { A = 6.34E+31 n = -4.66 E = 15.82
448     Ai= 1.71E+10 ni= 1.27 Ei= 11.33
449     fcA = 0.751 fctA = 12.1
450     fcb = 0.249 fctb = 10000
451     fcc = 1.0 fctc = 5493 }
452    
453     # Nguyen, Vereecken, Peeters 2006 - Total rate
454     # Rajak & Maiti 2010 - Branching ratios
455     G120f: C2H2 + O -> HCCO + H { A = 2.96E+09 n = 1.28 E = 10.34 }
456     G121f: C2H2 + O -> T-CH2 + CO { A = 7.40E+08 n = 1.28 E = 10.34 }
457    
458     # Tsang & Hampson 1986
459     # Modified for Collision Limit
460     G122f: C2H + OH -> C2H2 + O { A = 1.81E+13 n = .00 E = .00 }
461    
462     # Senosiain, Klippenstein & Miller 2005
463     # HCCOH lumped into CH2CO
464     G123f: C2H2 + OH -> C2H + H2O { A = 2.63E+06 n = 2.14 E = 71.38 }
465     G124f: C2H2 + OH -> CH2CO + H { A = 2.10E+01 n = 3.22 E = -1.76 }
466     G125f: C2H2 + OH -> CH3 + CO { A = 1.28E+09 n = 0.73 E = 10.79 }
467    
468     # Laskin & Wang 1999
469     G126f: C2H2 + M9 -> H2C2 + M9 { A = 2.45E+15 n = -0.64 E = 207.94 }
470     G127f: H2C2 + O2 -> 2 HCO { A = 1.00E+13 n = .00 E = .00 }
471    
472    
473     # Ketene
474     # ------
475     # Updated by Eiteneer & Frenklach 2003
476    
477     G128f: CH2CO + H -> HCCO + H2 { A = 5.00E+13 n = .00 E = 33.47 }
478     G129f: CH2CO + O -> HCCO + OH { A = 1.00E+13 n = .00 E = 33.47 }
479     G130f: CH2CO + OH -> HCCO + H2O { A = 7.50E+12 n = .00 E = 8.37 }
480     G131f: CH2CO + T-CH2 -> HCCO + CH3 { A = 3.60E+13 n = .00 E = 46.02 }
481    
482     # Woods & Haynes 1994
483     G132f: CH2CO + CH3 -> HCCO + CH4 { A = 7.50E+12 n = .00 E = 54.39 }
484     G133f: CH2CO + CH3 -> C2H5 + CO { A = 9.00E+10 n = .00 E = .00 }
485    
486     # Senosiain, Klippenstein & Miller 2006
487     G134f: CH2CO + H -> CH3 + CO { A = 7.77E+08 n = 1.45 E = 11.63 }
488    
489     # Lee & Bozzelli 2002
490     G135f: CH2CO + OH -> CH2OH + CO { A = 5.00E+12 n = .00 E = .00 }
491     G136f: CH2CO + T-CH2 -> C2H4 + CO { A = 1.00E+12 n = .00 E = .00 }
492    
493     G137f: CH2CO + O -> T-CH2 + CO2 { A = 1.75E+12 n = .00 E = 5.65 }
494    
495    
496     # Vinyl radical
497     # -------------
498    
499     G138f: C2H3 + H + M9 -> C2H4 + M9 { A = 1.40E+30 n = -3.86 E = 13.89
500     Ai= 6.08E+12 ni= 0.27 Ei= 1.17
501     fcA = 0.218 fctA = 207.5
502     fcb = 0.782 fctb = 2663
503     fcc = 1.0 fctc = 6095 }
504     G139f: C2H3 + H -> C2H2 + H2 { A = 3.00E+13 n = .00 E = .00 }
505    
506     # Harding, Klippenstein & Georgievskii 2005
507     G140f: C2H3 + O -> CH2CHO { A = 1.03E+13 n = 0.21 E = -1.79 }
508    
509     G141f: C2H3 + OH -> C2H2 + H2O { A = 5.00E+12 n = .00 E = .00 }
510     G142f: C2H3 + O2 -> C2H2 + HO2 { A = 1.34E+06 n = 1.61 E = -1.61 }
511    
512     # Stoliarov et al. 2002
513     G143f: C2H3 + CH3 -> C2H2 + CH4 { A = 9.03E+12 n = .00 E = -3.20 }
514    
515     G144f: C2H3 + O2 -> CH2CHO + O { A = 3.03E+11 n = 0.29 E = 0.05 }
516     G145f: C2H3 + O2 -> HCO + CH2O { A = 4.58E+16 n = -1.39 E = 4.25 }
517    
518     G146f: C2H3 + H2O2 -> C2H4 + HO2 { A = 1.21E+10 n = .00 E = -2.49 }
519     G147f: C2H3 + HCO -> C2H4 + CO { A = 9.00E+13 n = .00 E = .00 }
520    
521    
522     # CH2CHO
523     # ------
524    
525     # Senosiain, Klippenstein & Miller 2006
526     G148f: CH2CHO -> CH2CO + H { A = 1.32E+34 n = -6.57 E = 202.45 }
527     G149f: CH2CHO -> CH3 + CO { A = 6.51E+34 n = -6.87 E = 197.46 }
528    
529     # Same as for C2H5 + O
530     G150f: CH2CHO + O -> CH2O + HCO { A = 3.17E+13 n = 0.03 E = -1.65 }
531    
532     G151 : CH2CHO + O2 -> CH2O + CO + OH { A = 1.81E+10 n = .00 E = 0.00 }
533     G152 : CH2CHO + O2 -> 2 HCO + OH { A = 2.35E+10 n = .00 E = 0.00 }
534     G153f: CH2CHO + H -> CH2CO + H2 { A = 1.10E+13 n = .00 E = 0.00 }
535     G154f: CH2CHO + OH -> CH2CO + H2O { A = 1.20E+13 n = .00 E = 0.00 }
536    
537     G155f: CH2CHO + H -> CH3 + HCO { A = 2.20E+13 n = .00 E = 0.00 }
538     G156f: CH2CHO + OH -> CH2OH + HCO { A = 3.01E+13 n = .00 E = 0.00 }
539     G157f: CH2CHO + CH3 -> C2H5 + HCO { A = 4.90E+14 n = -0.50 E = .00 }
540    
541    
542     # Acetaldehyde
543     # ------------
544    
545     # Baulch et al. 2005 - HPL - Backward
546     # Modified for collision limit
547     G158f: CH3 + HCO -> CH3CHO { A = 5.00E+13 n = .00 E = .00 }
548    
549     G159f: CH3CHO + O -> CH2CHO + OH { A = 2.92E+12 n = .00 E = 7.57 }
550     G160f: CH3CHO + H -> CH2CHO + H2 { A = 2.05E+09 n = 1.16 E = 10.06 }
551    
552     G161 : CH3CHO + H -> CH3 + CO + H2 { A = 2.05E+09 n = 1.16 E = 10.06 }
553     G162 : CH3CHO + O -> CH3 + CO + OH { A = 2.92E+12 n = .00 E = 7.57 }
554     G163 : CH3CHO + OH -> CH3 + CO + H2O { A = 2.34E+10 n = .73 E = -4.66 }
555     G164 : CH3CHO + O2 -> CH3 + CO + HO2 { A = 3.01E+13 n = .00 E = 163.80 }
556     G165 : CH3CHO + HO2 -> CH3 + CO + H2O2 { A = 3.01E+12 n = .00 E = 49.89 }
557     G166 : CH3CHO + CH3 -> CH3 + CO + CH4 { A = 2.72E+06 n = 1.77 E = 24.77 }
558    
559    
560     # Ethylene
561     # --------
562    
563 gblanqu 2.1 # Ren, Davidson, Hanson 2012
564     G167f: C2H4 + M9 -> H2C2 + H2 + M9 { A = 2.60E+16 n = .00 E = 283.76 }
565 gblanqu 2.0
566     # Miller & Klippenstein 2004
567     # Refitted TROE form
568     G168f: C2H4 + H + M9 -> C2H5 + M9 { A = 2.03E+39 n = -6.64 E = 24.14
569     Ai= 1.37E+09 ni= 1.46 Ei= 5.67
570     fcA = 0.74 fctA = 361.7
571     fcb = 0.26 fctb = 10000
572     fcc = 1.0 fctc = 9096 }
573    
574     # Huynh, Panasewicz, Ratkiewicz, Truong 2007
575     # Closer to the recommendation of Baulch et al. 2005
576     G169f: C2H4 + H -> C2H3 + H2 { A = 1.27E+05 n = 2.75 E = 48.74 }
577    
578     # Nguyen, Vereecken, Hou, Nguyen, Peeters 2005
579     G170f: C2H4 + O -> CH2CHO + H { A = 7.66E+09 n = 0.88 E = 4.77 }
580     G171f: C2H4 + O -> T-CH2 + CH2O { A = 7.15E+04 n = 2.47 E = 3.89 }
581     G172f: C2H4 + O -> CH3 + HCO { A = 3.89E+08 n = 1.36 E = 3.71 }
582    
583     # Vasu, Hong, Davidson, Hanson, Golden 2010
584     G173f: C2H4 + OH -> C2H3 + H2O { A = 2.23E+04 n = 2.75 E = 9.27 }
585    
586     # Wang 2001
587     G174f: C2H4 + O2 -> C2H3 + HO2 { A = 4.22E+13 n = .00 E = 259.83 }
588     G175 : C2H4 + O2 -> CH3 + CO2 + H { A = 4.90E+12 n = 0.42 E = 317.15 }
589    
590     # Miller & Klippenstein 2013
591     G176f: C2H4 + CH3 -> C2H3 + CH4 { A = 2.06E-01 n = 3.94 E = 51.98 }
592    
593     G177f: C2H4 + CH3 + M9 -> N-C3H7 + M9 { A = 3.00E+63 n = -14.6 E = 76.02
594     Ai= 2.55E+06 ni= 1.60 Ei= 23.85
595     fcA = 0.8106 fctA = 277
596     fcb = 0.1894 fctb = 8748
597     fcc = 1.0 fctc = 7891 }
598    
599    
600     # Ethyl radical
601     # -------------
602    
603     G178f: C2H5 + H + M9 -> C2H6 + M9 { A = 1.99E+41 n = -7.08 E = 27.97
604     Ai= 5.21E+17 ni= -0.99 Ei= 6.61
605     fcA = 0.1578 fctA = 125
606     fcb = 0.8422 fctb = 2219
607     fcc = 1.0 fctc = 6882 }
608    
609     G179f: C2H5 + H -> C2H4 + H2 { A = 2.00E+12 n = .00 E = .00 }
610    
611     # Miller, Klippenstein & Robertson 2000
612     G180f: C2H5 + O2 -> C2H4 + HO2 { A = 1.92E+07 n = 1.02 E = -8.51 }
613    
614     # Zhu, Xu & Lin 2004
615     G181f: C2H5 + CH3 -> C2H4 + CH4 { A = 1.18E+04 n = 2.45 E = 12.22 }
616    
617     # Harding, Klippenstein & Georgievskii 2005
618     G182f: C2H5 + O -> CH3 + CH2O { A = 3.17E+13 n = 0.03 E = -1.65 }
619    
620     # Ludwig et al. 2006
621     G183f: C2H5 + HO2 -> C2H5O + OH { A = 3.10E+13 n = .00 E = .00 }
622    
623     G184f: C2H5 + HCO -> C2H6 + CO { A = 1.20E+14 n = .00 E = .00 }
624     G185f: C2H5 + HO2 -> C2H6 + O2 { A = 3.00E+11 n = .00 E = .00 }
625     G186f: C2H5 + HO2 -> C2H4 + H2O2 { A = 3.00E+11 n = .00 E = .00 }
626    
627    
628     # Ethoxy radical
629     # --------------
630    
631     # Dames 2014
632     G187f: C2H5O + M9 -> CH3 + CH2O + M9 { A = 4.70E+25 n = -3.00 E = 69.17
633     Ai= 6.31E+10 ni= 0.93 Ei= 71.54
634     fcA = 0.574 fctA = 0.3
635     fcb = 0.426 fctb = 2046
636     fcc = 1.0 fctc = 1e5 }
637    
638     # Baulch et al. 2005
639     G188f: C2H5O + O2 -> CH3CHO + HO2 { A = 2.29E+10 n = .00 E = 3.66 }
640    
641    
642     # Ethane
643     # ------
644    
645     # Oehlschlaeger et al. 2005
646     G189f: C2H6 + M9 -> 2 CH3 + M9 { A = 3.72E+65 n =-13.14 E = 425.01
647     Ai= 1.88E+50 ni= -9.72 Ei= 449.12
648     fcA = 0.61 fctA = 100
649     fcb = 0.39 fctb = 1900
650     fcc = 1.0 fctc = 6000 }
651    
652     # Chakraborty, Zhao, Lin, & Truhlar 2006
653     # Fit 500-2000K
654     G190f: C2H6 + H -> C2H5 + H2 { A = 1.70E+05 n = 2.70 E = 24.02 }
655    
656     # Huynh, Zhang, Truong 2008
657     G191f: C2H6 + O -> C2H5 + OH { A = 3.17E+01 n = 3.80 E = 13.10 }
658    
659     # Krasnoperov & Michael 2004
660     G192f: C2H6 + OH -> C2H5 + H2O { A = 1.61E+06 n = 2.22 E = 3.10 }
661    
662     # Carstensen & Dean 2005
663     G193f: C2H6 + HO2 -> C2H5 + H2O2 { A = 2.61E+02 n = 3.37 E = 66.58 }
664    
665     G194f: C2H6 + S-CH2 -> C2H5 + CH3 { A = 4.00E+13 n = .00 E = -2.30 }
666    
667     # Peukert, Labbe, Sivaramakrishnan, Michael 2013
668     G195f: C2H6 + CH3 -> C2H5 + CH4 { A = 3.45E+01 n = 3.44 E = 43.47 }
669    
670    
671     # Propyl radicals
672     # ---------------
673    
674    
675     # Curran 2006 - HPL
676     G196f: C3H6 + H + M9 -> N-C3H7 + M9 { A = 6.26E+38 n = -6.66 E = 29.29
677     Ai= 2.50E+11 ni= 0.51 Ei= 10.96
678     fcA = 0.0 fctA = 1000
679     fcb = 1.0 fctb = 1310
680     fcc = 1.0 fctc = 48097 }
681     G197f: C3H6 + H + M9 -> I-C3H7 + M9 { A = 8.70E+42 n = -7.50 E = 19.75
682     Ai= 4.24E+11 ni= 0.51 Ei= 5.15
683     fcA = 0.0 fctA = 1000
684     fcb = 1.0 fctb = 645.4
685     fcc = 1.0 fctc = 6844.3 }
686    
687     G198f: N-C3H7 + H -> C2H5 + CH3 { A = 3.70E+24 n = -2.92 E = 52.32 }
688     G199f: I-C3H7 + H -> C2H5 + CH3 { A = 1.40E+28 n = -3.94 E = 66.59 }
689     G200f: N-C3H7 + H -> C3H6 + H2 { A = 1.80E+12 n = .00 E = .00 }
690     G201f: I-C3H7 + H -> C3H6 + H2 { A = 3.20E+12 n = .00 E = .00 }
691     G202f: N-C3H7 + O -> C2H5 + CH2O { A = 9.60E+13 n = .00 E = .00 }
692     G203f: I-C3H7 + O -> CH3CHO + CH3 { A = 9.60E+13 n = .00 E = .00 }
693     G204f: N-C3H7 + OH -> C3H6 + H2O { A = 2.41E+13 n = .00 E = .00 }
694     G205f: I-C3H7 + OH -> C3H6 + H2O { A = 2.41E+13 n = .00 E = .00 }
695    
696     # DeSain, Miller, Klippenstein & Taatjes 2003
697     G206f: N-C3H7 + O2 -> C3H6 + HO2 { A = 3.70E+16 n = -1.63 E = 14.30 }
698     G207f: I-C3H7 + O2 -> C3H6 + HO2 { A = 6.70E+20 n = -3.02 E = 10.48 }
699    
700     # Knyazev & Slagle 2001 - Total rate
701     # Shafir, Slagle & Knyazev 2003 - Branching ratio
702     G208f: N-C3H7 + CH3 -> C3H6 + CH4 { A = 3.31E+12 n = .00 E = -3.22 }
703    
704    
705     # Propane
706     # -------
707    
708     # From Tsang 1988
709     G209f: N-C3H7 + H + M9 -> C3H8 + M9 { A = 4.42E+61 n =-13.55 E = 47.52
710     Ai= 3.61E+13 ni= .00 Ei= .00
711     fcA = 0.685 fctA = 369
712     fcb = 0.315 fctb = 3285
713     fcc = 1.0 fctc = 6667 }
714     G210f: I-C3H7 + H + M9 -> C3H8 + M9 { A = 1.70E+58 n =-12.08 E = 47.13
715     Ai= 2.40E+13 ni= .00 Ei= .00
716     fcA = 0.502 fctA = 1314
717     fcb = 0.498 fctb = 1314
718     fcc = 1.0 fctc = 50000 }
719    
720     # Oehlschlaeger et al. 2005
721     G211f: C3H8 + M9 -> C2H5 + CH3 + M9 { A = 5.64E+74 n =-15.74 E = 413.04
722     Ai= 1.29E+37 ni= -5.84 Ei= 407.47
723     fcA = 0.69 fctA = 50
724     fcb = 0.31 fctb = 3000
725     fcc = 1.0 fctc = 9000 }
726     # Carstensen & Dean 2009
727     G212f: C3H8 + H -> N-C3H7 + H2 { A = 9.36E+07 n = 1.97 E = 34.31 }
728     G213f: C3H8 + H -> I-C3H7 + H2 { A = 7.60E+07 n = 1.86 E = 23.43 }
729    
730     G214f: C3H8 + O -> N-C3H7 + OH { A = 1.90E+05 n = 2.68 E = 15.55 }
731     G215f: C3H8 + O -> I-C3H7 + OH { A = 4.76E+04 n = 2.71 E = 08.81 }
732    
733     # Sivaramkrishnan, Srinivasan, Su, Michael 2009
734     G216f: C3H8 + OH -> N-C3H7 + H2O { A = 5.15E+03 n = 2.94 E = -1.75 }
735     G217f: C3H8 + OH -> I-C3H7 + H2O { A = 1.81E+05 n = 2.44 E = -2.24 }
736    
737     G218f: C3H8 + CH3 -> N-C3H7 + CH4 { A = 9.03E-01 n = 3.65 E = 29.93 }
738     G219f: C3H8 + CH3 -> I-C3H7 + CH4 { A = 1.51E+00 n = 3.46 E = 29.93 }
739     G220f: C3H8 + HO2 -> N-C3H7 + H2O2 { A = 4.76E+04 n = 2.55 E = 69.00 }
740     G221f: C3H8 + HO2 -> I-C3H7 + H2O2 { A = 9.63E+03 n = 2.60 E = 58.20 }
741    
742    
743    
744     #=========================================================================#
745     # #
746     # "Experimental and Modeling Study of Shock-Tube Oxidation of Acetylene" #
747     # B. Eiteneer and M. Frenklach #
748     # Int. J. Chem. Kinet. 35, 391:414 (2003) #
749     # #
750     #=========================================================================#
751    
752    
753     # Propynylidene
754     # -------------
755    
756     R005f: C3H2 + O -> C3H2O { A = 1.36E+14 n = .00 E = .00 }
757     R006f: C3H2 + OH -> C2H2 + HCO { A = 1.00E+13 n = .00 E = .00 }
758     R007f: C3H2 + O2 -> HCCO + CO + H { A = 1.25E+11 n = .00 E = 4.18 }
759     R008f: C3H2 + CH -> C4H2 + H { A = 5.00E+13 n = .00 E = .00 }
760     R009f: C3H2 + T-CH2 -> N-C4H3 + H { A = 5.00E+13 n = .00 E = .00 }
761     R010f: C3H2 + CH3 -> C4H4 + H { A = 5.00E+12 n = .00 E = .00 }
762     R011f: C3H2 + HCCO -> N-C4H3 + CO { A = 1.00E+13 n = .00 E = .00 }
763    
764    
765     # Propynal
766     # --------
767    
768     # Estimated
769     R012f: C2H + HCO -> C3H2O { A = 5.00E+13 n = .00 E = .00 }
770     # From P-C3H4 + H
771     R013f: C3H2O + H -> C2H2 + HCO { A = 3.46E+12 n = 0.44 E = 22.86 }
772    
773     # Taken from CH3CHO
774     R014 : C3H2O + H -> C2H + CO + H2 { A = 2.05E+09 n = 1.16 E = 10.06 }
775     R015 : C3H2O + O -> C2H + CO + OH { A = 2.92E+12 n = .00 E = 7.57 }
776     R016 : C3H2O + O2 -> C2H + CO + HO2 { A = 3.01E+13 n = .00 E = 163.80 }
777     R017 : C3H2O + OH -> C2H + CO + H2O { A = 2.34E+10 n = .73 E = -4.66 }
778     R018 : C3H2O + HO2 -> C2H + CO + H2O2 { A = 3.01E+12 n = .00 E = 49.89 }
779     R019 : C3H2O + CH3 -> C2H + CO + CH4 { A = 2.72E+06 n = 1.77 E = 24.77 }
780    
781    
782     # Propargyl radical
783     # -----------------
784    
785     R020f: C2H2 + HCCO -> C3H3 + CO { A = 1.00E+11 n = .00 E = 12.55 }
786    
787     # Tsang & Hampson 1986
788     R021f: C2H + CH3 -> C3H3 + H { A = 2.41E+13 n = .00 E = .00 }
789    
790     # Polino, Klippenstein, Harding, Georgievskii 2013
791     R022f: C2H2 + S-CH2 -> C3H3 + H { A = 3.97E+15 n = -0.57 E = -0.02 }
792    
793     # 2x rate for C2H3+H
794     R023f: C3H2 + H + M9 -> C3H3 + M9 { A = 2.80E+30 n = -3.86 E = 13.89
795     Ai= 1.02E+13 ni= .27 Ei= 1.17
796     fcA = 0.218 fctA = 207.5
797     fcb = 0.782 fctb = 2663
798     fcc = 1.0 fctc = 6095 }
799    
800     # Miller & Klippenstein 2003 (1bar)
801     R024f: C3H3 + H -> C3H2 + H2 { A = 1.10E+10 n = 1.13 E = 58.28 }
802    
803     # Adapted from C2H2 + OH
804     R025f: C3H3 + OH -> C2H3CHO { A = 2.10E+01 n = 3.22 E = -1.76 }
805     R026f: C3H3 + OH -> C2H4 + CO { A = 1.28E+09 n = 0.73 E = 10.79 }
806    
807     # 1/2 rate for C2H4+OH
808     R027f: C3H3 + OH -> C3H2 + H2O { A = 1.13E+05 n = 2.28 E = 10.32 }
809    
810     # Lee, Nam & Choi 2006
811     # Kwon, Nam, Youn, Joo, Lee, & Choi 2006
812     # Slagle, Gmurczyk, Batt & Gutman 1991
813     R029f: C3H3 + O -> C3H2O + H { A = 1.38E+14 n = .00 E = .00 }
814    
815     # Hahn, Klippenstein, Miller 2001
816     R030f: C3H3 + O2 -> CH2CO + HCO { A = 1.70E+05 n = 1.70 E = 6.28 }
817    
818     R031 : C3H3 + HO2 -> C2H3 + CO + OH { A = 8.00E+11 n = .00 E = .00 }
819    
820     # Wang 2001
821     R032f: C3H3 + HO2 -> A-C3H4 + O2 { A = 3.00E+11 n = .00 E = .00 }
822     R033f: C3H3 + HO2 -> P-C3H4 + O2 { A = 3.00E+11 n = .00 E = .00 }
823     R034f: P-C3H4 + O2 -> CH3 + HCO + CO { A = 4.00E+14 n = .00 E = 175.43 }
824    
825     R035f: C3H3 + HCO -> A-C3H4 + CO { A = 2.50E+13 n = .00 E = .00 }
826     R036f: C3H3 + HCO -> P-C3H4 + CO { A = 2.50E+13 n = .00 E = .00 }
827     R037f: C3H3 + CH -> I-C4H3 + H { A = 5.00E+13 n = .00 E = .00 }
828    
829     # Miller, Melius 1992
830     R038f: C3H3 + T-CH2 -> C4H4 + H { A = 5.00E+13 n = .00 E = .00 }
831    
832    
833     # Propyne & Allene
834     # ----------------
835    
836     # Thiesemann, Clifford, Taatjes, Klippenstein 2001
837     # Zhang, Maksyutenko, Kaiser 2012
838     R200f: C2H4 + CH -> A-C3H4 + H { A = 9.98E+14 n = -0.31 E = .00 }
839    
840     # Miller & Klippenstein 2003 (1bar)
841     R039f: A-C3H4 -> P-C3H4 { A = 7.76E+39 n = -7.80 E = 328.22 }
842    
843     # Giri, Fernandes, Bentz, Hippler, Olzmann 2011
844     R040f: P-C3H4 + M0 -> C3H3 + H + M0 { A = 2.15E+43 n = -6.81 E = 420.61 }
845     R041f: A-C3H4 + M0 -> C3H3 + H + M0 { A = 2.15E+43 n = -6.81 E = 420.61 }
846    
847     # Miller, Senosiain, Klippenstein, Georgievskii 2008
848     # Refitted 800K-2500K - 1bar
849     R042f: A-C3H4 + H -> C2H2 + CH3 { A = 8.95E+13 n = -0.02 E = 47.07 }
850    
851     # Sheen, Rosado-Reyes, Tsang 2013
852     R043f: C2H2 + CH3 -> P-C3H4 + H { A = 1.48E+11 n = 0.60 E = 59.86 }
853     R044f: P-C3H4 + H -> A-C3H4 + H { A = 1.58E+18 n = -1.00 E = 50.72 }
854    
855     # Miller, Senosiain, Klippenstein, Georgievskii 2008
856     # P=1bar
857     R045f: A-C3H4 + H -> A-C3H5 { A = 2.01E+49 n =-10.77 E = 82.10 }
858     R046f: A-C3H4 + H -> T-C3H5 { A = 6.70E+42 n =-12.46 E = 68.45 }
859     R047f: P-C3H4 + H -> T-C3H5 { A = 8.83E+52 n =-12.36 E = 68.81 }
860     R048f: P-C3H4 + H -> S-C3H5 { A = 1.53E+49 n =-11.97 E = 59.18 }
861    
862     # 1/2 the rate for C2H6
863     R049f: P-C3H4 + H -> C3H3 + H2 { A = 8.50E+04 n = 2.70 E = 24.02 }
864     R050f: P-C3H4 + O -> C3H3 + OH { A = 1.59E+01 n = 3.80 E = 13.10 }
865     R051f: P-C3H4 + OH -> C3H3 + H2O { A = 8.05E+05 n = 2.22 E = 3.10 }
866     R052f: P-C3H4 + CH3 -> C3H3 + CH4 { A = 1.73E+01 n = 3.44 E = 43.47 }
867     R053f: P-C3H4 + HO2 -> C3H3 + H2O2 { A = 1.30E+02 n = 3.37 E = 66.58 }
868    
869     # Same as for C2H4
870     R054f: A-C3H4 + H -> C3H3 + H2 { A = 1.33E+06 n = 2.53 E = 51.21 }
871     R055f: A-C3H4 + OH -> C3H3 + H2O { A = 1.31E-01 n = 4.20 E = -3.60 }
872     R056f: A-C3H4 + CH3 -> C3H3 + CH4 { A = 2.27E+05 n = 2.00 E = 38.49 }
873     R057f: A-C3H4 + HO2 -> C3H3 + H2O2 { A = 9.76E+10 n = 0.12 E = 97.78 }
874    
875     # Nguyen, Peeters & Vereecken 2006
876     # Total rate assigned
877     R058f: A-C3H4 + O -> CH2CO + T-CH2 { A = 9.63E+06 n = 2.05 E = 0.75 }
878    
879     # Adapted from C2H2+O
880     # Zhao, Wu, Zhao et al. 2009 - Products
881     R059f: P-C3H4 + O -> C2H4 + CO { A = 3.70E+09 n = 1.28 E = 10.34 }
882    
883     # From C2H2 + OH
884     R060f: P-C3H4 + OH -> CH2CO + CH3 { A = 2.10E+01 n = 3.22 E = -1.76 }
885     R061f: P-C3H4 + OH -> C2H5 + CO { A = 1.28E+09 n = 0.73 E = 10.79 }
886    
887     R062f: A-C3H4 + C2H -> C2H2 + C3H3 { A = 1.00E+13 n = .00 E = .00 }
888     R063f: P-C3H4 + C2H -> C2H2 + C3H3 { A = 1.00E+13 n = .00 E = .00 }
889    
890     # Liu, Maluc, Jonah 1988
891     R064f: A-C3H4 + OH -> CH2CO + CH3 { A = 4.03E+12 n = .00 E = -0.83 }
892    
893    
894     # Propenal
895     # --------
896    
897     R065f: C2H3 + HCO -> C2H3CHO { A = 1.80E+13 n = .00 E = .00 }
898    
899     # Baulch et al. 2005 - adapted from CH3CHO
900     R066 : C2H3CHO + H -> C2H3 + CO + H2 { A = 4.09E+09 n = 1.16 E = 10.06 }
901     R067 : C2H3CHO + O -> C2H3 + CO + OH { A = 5.84E+12 n = .00 E = 7.57 }
902     R068 : C2H3CHO + OH -> C2H3 + CO + H2O { A = 2.89E+08 n = 1.35 E = -6.58 }
903     R069 : C2H3CHO + HO2 -> C2H3 + CO + H2O2 { A = 4.09E+04 n = 2.50 E = 42.69 }
904     R070 : C2H3CHO + CH3 -> C2H3 + CO + CH4 { A = 3.49E-08 n = 6.21 E = 6.82 }
905    
906    
907     # Allyl radicals
908     # --------------
909    
910     # Miller, Senosiain, Klippenstein, Georgievskii 2008
911     # Refitted 800K-2500K - P=1bar
912     R071f: C2H2 + CH3 -> S-C3H5 { A = 7.45E+43 n =-10.13 E = 77.50 }
913    
914     # Davis, Law, Wang 1999 (1bar)
915     R072f: A-C3H5 -> T-C3H5 { A = 7.06E+56 n =-14.08 E = 317.43 }
916     R073f: A-C3H5 -> S-C3H5 { A = 5.00E+51 n =-13.02 E = 306.69 }
917     R074f: T-C3H5 -> S-C3H5 { A = 1.50E+48 n =-12.71 E = 225.52 }
918    
919     # Klippenstein, Harding, Georgievskii, Miller 2008
920     # Fitted 400K-2500K
921     R075f: A-C3H5 + H -> A-C3H4 + H2 { A = 9.56E+03 n = 2.80 E = 13.77 }
922    
923     # Tsang 1991
924     R076f: A-C3H5 + OH -> A-C3H4 + H2O { A = 6.03E+12 n = .00 E = .00 }
925     R077f: A-C3H5 + CH3 -> A-C3H4 + CH4 { A = 3.01E+12 n = -0.32 E = -0.55 }
926     R078f: A-C3H5 + C2H3 -> A-C3H4 + C2H4 { A = 2.41E+12 n = .00 E = .00 }
927     R079f: A-C3H5 + C2H5 -> A-C3H4 + C2H6 { A = 9.64E+11 n = .00 E = -0.55 }
928    
929     # Lee & Bozzelli 2005
930     R081f: A-C3H5 + O2 -> A-C3H4 + HO2 { A = 2.06E+04 n = 2.19 E = 73.60 }
931     R082f: A-C3H5 + O2 -> C2H3CHO + OH { A = 3.36E+05 n = 1.81 E = 80.29 }
932     R083 : A-C3H5 + O2 -> C2H2 + CH2O + OH { A = 9.71E+20 n = -2.70 E = 104.52 }
933     R084f: A-C3H5 + O2 -> CH2CHO + CH2O { A = 3.08E+09 n = 0.37 E = 70.75 }
934    
935     # Estimated from C2H5+O
936     # Park, lee, Choi 2003 - Products
937     R085f: A-C3H5 + O -> C2H3CHO + H { A = 3.17E+13 n = 0.03 E = -1.65 }
938    
939     R086 : A-C3H5 + OH -> C2H3CHO + H2 { A = 4.20E+32 n = -5.16 E = 126.05 }
940     R087f: A-C3H5 + HCO -> C3H6 + CO { A = 6.00E+13 n = .00 E = .00 }
941     R088f: A-C3H5 + HO2 -> C3H6 + O2 { A = 2.66E+12 n = .00 E = .00 }
942     # From A1CH2+HO2
943     R089f: A-C3H5 + HO2 -> C3H5O + OH { A = 1.19E+09 n = 1.03 E = -9.41 }
944    
945     R090f: T-C3H5 + H -> P-C3H4 + H2 { A = 3.34E+12 n = .00 E = .00 }
946     R091f: T-C3H5 + O -> CH3 + CH2CO { A = 6.00E+13 n = .00 E = .00 }
947     R092 : T-C3H5 + OH -> CH3 + CH2CO + H { A = 5.00E+12 n = .00 E = .00 }
948     R093 : T-C3H5 + HO2 -> CH3 + CH2CO + OH { A = 2.00E+13 n = .00 E = .00 }
949     R094f: T-C3H5 + HCO -> C3H6 + CO { A = 9.00E+13 n = .00 E = .00 }
950     R095f: T-C3H5 + CH3 -> P-C3H4 + CH4 { A = 1.00E+11 n = .00 E = .00 }
951    
952     R096f: S-C3H5 + H -> P-C3H4 + H2 { A = 3.34E+12 n = .00 E = .00 }
953     R097f: S-C3H5 + O -> C2H4 + HCO { A = 6.00E+13 n = .00 E = .00 }
954     R098 : S-C3H5 + OH -> C2H4 + HCO + H { A = 5.00E+12 n = .00 E = .00 }
955     R099 : S-C3H5 + HO2 -> C2H4 + HCO + OH { A = 2.00E+13 n = .00 E = .00 }
956     R100f: S-C3H5 + HCO -> C3H6 + CO { A = 9.00E+13 n = .00 E = .00 }
957     R101f: S-C3H5 + CH3 -> P-C3H4 + CH4 { A = 1.00E+11 n = .00 E = .00 }
958    
959     # Adapted from C2H5/C2H3+O2
960     R102f: T-C3H5 + O2 -> A-C3H4 + HO2 { A = 1.92E+07 n = 1.02 E = -8.51 }
961     R103f: T-C3H5 + O2 -> P-C3H4 + HO2 { A = 1.34E+06 n = 1.61 E = -1.61 }
962     R104f: S-C3H5 + O2 -> P-C3H4 + HO2 { A = 6.70E+05 n = 1.61 E = -1.61 }
963     R105 : T-C3H5 + O2 -> CH3 + CO + CH2O { A = 4.58E+16 n = -1.39 E = 4.25 }
964     R106f: S-C3H5 + O2 -> CH3CHO + HCO { A = 4.58E+16 n = -1.39 E = 4.25 }
965    
966    
967     # Propanone
968     # ---------
969    
970     # NC7 path from LLNL
971     R107f: C3H5O -> C2H3CHO + H { A = 1.00E+14 n = .00 E = 121.75 }
972     R108f: C3H5O -> C2H3 + CH2O { A = 2.03E+12 n = 0.09 E = 98.58 }
973     R109f: C3H5O + O2 -> C2H3CHO + HO2 { A = 1.00E+12 n = .00 E = 25.10 }
974    
975    
976     # Propene
977     # -------
978     # A -> 60%-85% C2H6; S -> 20%-50% C2H4; T -> 35% C2H4
979    
980     # Stoliarov et al. 2002
981     # Rates fitted at 1.33 bar - 500K to 2400K
982     R110f: C3H6 -> C2H3 + CH3 { A = 4.04E+42 n = -7.67 E = 467.90 }
983     R111f: C2H3 + CH3 -> A-C3H5 + H { A = 1.93E+18 n = -1.25 E = 32.09 }
984    
985     # Harding, Klippenstein, & Georgievskii 2007
986     # -> High pressure limit
987     # Stoliarov et al. 2002
988     # -> Fall-off at 1.33bar - 900K to 3000K
989     R112f: A-C3H5 + H -> C3H6 { A = 5.93E+54 n =-11.76 E = 98.53 }
990    
991     # Miller & Klippenstein 2013
992     # Refitted at P=1bar
993     R113f: C3H6 + H -> C2H4 + CH3 { A = 2.67E+12 n = 0.47 E = 22.72 }
994     R114f: C3H6 + H -> A-C3H5 + H2 { A = 1.42E+04 n = 2.82 E = 14.23 }
995     R115f: C3H6 + H -> S-C3H5 + H2 { A = 8.34E+02 n = 3.25 E = 50.86 }
996     R116f: C3H6 + H -> T-C3H5 + H2 { A = 1.49E+02 n = 3.38 E = 37.28 }
997    
998     # Zador, Jasper, Miller 2009
999     # Vasu, Hong, Davidson, Hanson 2010
1000     R117f: C3H6 + OH -> A-C3H5 + H2O { A = 9.00E+04 n = 2.59 E = 1.74 }
1001     R118f: C3H6 + OH -> S-C3H5 + H2O { A = 3.67E+03 n = 2.89 E = 8.05 }
1002     R119f: C3H6 + OH -> T-C3H5 + H2O { A = 4.67E+04 n = 2.47 E = 7.31 }
1003    
1004     # Adapted from C2H4 - To be revised later
1005     R120f: C3H6 + O -> CH2CHO + CH3 { A = 5.09E+07 n = 1.66 E = 2.75 }
1006     R121f: C3H6 + O -> C2H5 + HCO { A = 1.95E+08 n = 1.36 E = 3.71 }
1007     R122 : C3H6 + O -> C2H3CHO + 2H { A = 3.83E+09 n = 0.88 E = 4.77 }
1008    
1009     # Rate from C3H8 + X (x0.5)
1010     R123f: C3H6 + O -> A-C3H5 + OH { A = 9.95E+04 n = 2.68 E = 15.55 }
1011     R124f: C3H6 + HO2 -> A-C3H5 + H2O2 { A = 2.38E+04 n = 2.55 E = 69.00 }
1012     R125f: C3H6 + CH3 -> A-C3H5 + CH4 { A = 4.57E-01 n = 3.65 E = 29.93 }
1013    
1014     # From C2H4
1015     R126f: C3H6 + CH3 -> S-C3H5 + CH4 { A = 1.14E+05 n = 2.00 E = 38.49 }
1016     R127f: C3H6 + CH3 -> T-C3H5 + CH4 { A = 5.68E+05 n = 2.00 E = 38.49 }
1017    
1018    
1019     # Hexadiyene
1020     # ----------
1021    
1022     # Lynch, Annesley, Aul, Yang, Tranter 2013
1023     R128f: A-C3H5 + A-C3H5 -> A-C3H4 + C3H6 { A = 7.50E+11 n = .00 E = .00 }
1024     # Matsugi, Suma, Miyoshi 2011
1025     R129 : A-C3H5 + A-C3H5 -> C6H10 { A = 3.18E+13 n = -0.24 E = -2.46 }
1026    
1027     # From C3H8 (x2)
1028     R130 : C6H10 + H -> C6H9 + H2 { A = 1.52E+08 n = 1.86 E = 23.43 }
1029     R131 : C6H10 + O -> C6H9 + OH { A = 9.52E+04 n = 2.71 E = 8.81 }
1030     R132 : C6H10 + OH -> C6H9 + H2O { A = 3.62E+05 n = 2.44 E = -2.24 }
1031     R133 : C6H10 + CH3 -> C6H9 + CH4 { A = 3.02E+00 n = 3.46 E = 29.93 }
1032     R134 : C6H10 + HO2 -> C6H9 + H2O2 { A = 1.93E+04 n = 2.60 E = 58.20 }
1033    
1034     # From C3H6 (x2)
1035     R135 : C6H10 + H -> C4H7 + C2H4 { A = 5.34E+12 n = 0.47 E = 22.72 }
1036    
1037    
1038     # Hexadiyenyl radical
1039     # -------------------
1040    
1041     # From C2H5
1042     R136 : C6H9 + O -> C2H3CHO + A-C3H5 { A = 3.17E+13 n = 0.03 E = -1.65 }
1043     R137 : C6H9 + HO2 -> C2H3CHO + A-C3H5 + OH { A = 3.10E+13 n = .00 E = .00 }
1044    
1045     # From LLNL
1046     R138 : C6H9 -> C4H6 + C2H3 { A = 2.50E+13 n = .00 E = 188.28 }
1047    
1048    
1049    
1050     #==========================================================================#
1051     # #
1052     # "Shock-Tube and Modeling Study of Diacetylene Pyrolysis and Oxidation" #
1053     # Y. Hidaka, Y. Henmi, T. Ohonishi & T. Okuno #
1054     # Combustion and Flame 130:62-82 (2002) #
1055     # #
1056     #==========================================================================#
1057    
1058    
1059     # Diacetylene
1060     # -----------
1061    
1062     # From C2H
1063     H01 : C4H + O2 -> C2H + 2CO { A = 1.00E+13 n = .00 E = -3.16 }
1064    
1065     # HT backward rate (1900K) as Frank, Just 1980
1066     # Xu, Braun-Unkhoff, Naumann, Frank 2007
1067     H02f: C4H + H -> C4H2 { A = 3.00E+14 n = .00 E = .00 }
1068    
1069     # Adapted from C2H2
1070     H03f: C4H2 + H -> C4H + H2 { A = 3.20E+09 n = 1.80 E = 125.97 }
1071    
1072     # Estimated
1073     H04f: C2H + C2H -> C4H2 { A = 1.00E+14 n = .00 E = .00 }
1074    
1075     # Ceursters, Nguyen, Peeters, Nguyen 2000
1076     H05f: C2H2 + C2H -> C4H2 + H { A = 7.80E+13 n = .00 E = .00 }
1077    
1078     # From P-C3H4 (x2)
1079     H06 : C4H2 + O2 -> C2H + CO + HCO { A = 8.00E+14 n = .00 E = 175.43 }
1080    
1081     # Mitchell, Brunning, Payne, Stief 1988
1082     # Rate about x10 that of C2H2 at 298K
1083     # TO BE REVISED
1084     H07f: C4H2 + O -> C3H2 + CO { A = 3.70E+09 n = 1.28 E = 10.34 }
1085    
1086     # Klippenstein & Miller 2005
1087     # Refitted Rate & TROE form
1088     H08f: C4H2 + H + M9 -> I-C4H3 + M9 { Ai= 4.31E+10 ni= 1.16 Ei= 7.33
1089     A = 2.30E+45 n = -8.10 E = 10.49
1090     fcA = 0.901 fctA = 12.5
1091     fcB = 0.099 fctB = 10000
1092     fcc = 1.0 fctc = 6674 }
1093     H09f: C4H2 + H -> N-C4H3 { A = 1.37E+39 n = -7.87 E = 64.61 }
1094    
1095     # Senosiain, Klippenstein & Miller 2007
1096     H10f: C4H2 + OH -> C4H + H2O { A = 9.15E+09 n = 1.03 E = 90.99 }
1097     H11f: C4H2 + OH -> C4H2O + H { A = 3.41E+10 n = 0.31 E = 5.00 }
1098     H12f: C4H2 + OH -> C3H3 + CO { A = 2.11E+23 n = -3.47 E = 31.76 }
1099    
1100    
1101     # Ethynylketene
1102     # -------------
1103    
1104     # From C4H2+H/OH (HPLx0.5)
1105     H13f: C4H2O + H -> C2H2 + HCCO { A = 6.85E+38 n = -7.87 E = 64.61 }
1106     H14f: C4H2O + OH -> CH2CO + HCCO { A = 1.53E+11 n = 0.47 E = -1.95 }
1107    
1108    
1109     # C4H3 radicals
1110     # -------------
1111    
1112     # Wang & Frenklach 1994 ??
1113     H15f: N-C4H3 -> I-C4H3 { A = 4.10E+43 n = -9.50 E = 221.75 }
1114     H16f: N-C4H3 + H -> I-C4H3 + H { A = 2.50E+20 n = -1.67 E = 45.19 }
1115     H17f: N-C4H3 + H -> C4H4 { A = 2.00E+47 n =-10.26 E = 54.68 }
1116     H18f: I-C4H3 + H -> C4H4 { A = 3.40E+43 n = -9.01 E = 50.71 }
1117     H19f: N-C4H3 + H -> C2H2 + H2C2 { A = 6.30E+25 n = -3.34 E = 41.88 }
1118     H20f: I-C4H3 + H -> C2H2 + H2C2 { A = 2.80E+23 n = -2.55 E = 45.10 }
1119    
1120     # From C2H3+X
1121     H21f: N-C4H3 + H -> C4H2 + H2 { A = 1.50E+13 n = .00 E = .00 }
1122     H22f: I-C4H3 + H -> C4H2 + H2 { A = 3.00E+13 n = .00 E = .00 }
1123     H23f: N-C4H3 + OH -> C4H2 + H2O { A = 2.50E+12 n = .00 E = .00 }
1124     H24f: I-C4H3 + OH -> C4H2 + H2O { A = 5.00E+12 n = .00 E = .00 }
1125     H25f: N-C4H3 + O2 -> C4H2 + HO2 { A = 6.70E+05 n = 1.61 E = -1.61 }
1126     H26f: I-C4H3 + O2 -> C4H2 + HO2 { A = 1.34E+06 n = 1.61 E = -1.61 }
1127    
1128     H27f: I-C4H3 + O -> CH2CO + C2H { A = 2.00E+13 n = .00 E = .00 }
1129     H28f: I-C4H3 + O2 -> HCCO + CH2CO { A = 1.63E+11 n = .00 E = -7.53 }
1130    
1131     # From C3H3 + O2
1132     H29f: I-C4H3 + O2 -> HCO + C2H2 + CO { A = 1.70E+05 n = 1.70 E = 6.28 }
1133    
1134    
1135     # Vinylacetylene
1136     # --------------
1137    
1138     # Decomposition of C4H4 revisited
1139     # Problem for diffusion flamelets with C2H2+H2C2
1140     H30f: C2H3 + C2H -> C4H4 { A = 1.00E+14 n = .00 E = .00 }
1141     H31f: C2H4 + C2H -> C4H4 + H { A = 1.20E+13 n = .00 E = .00 }
1142    
1143     # Miller, Klippenstein & Robertson 2000
1144     H32f: C2H3 + C2H2 -> C4H4 + H { A = 1.32E+12 n = 0.16 E = 34.78 }
1145    
1146     # Adapted from C2H4 - 3kcal
1147     H33f: C4H4 + H -> N-C4H3 + H2 { A = 1.27E+05 n = 2.75 E = 48.74 }
1148     H34f: C4H4 + H -> I-C4H3 + H2 { A = 6.35E+04 n = 2.75 E = 36.19 }
1149     H35f: C4H4 + OH -> N-C4H3 + H2O { A = 2.23E+04 n = 2.75 E = 9.27 }
1150     H36f: C4H4 + OH -> I-C4H3 + H2O { A = 1.12E+04 n = 2.75 E = -3.28 }
1151     H37f: C4H4 + CH3 -> N-C4H3 + CH4 { A = 1.14E+05 n = 2.00 E = 38.49 }
1152     H38f: C4H4 + CH3 -> I-C4H3 + CH4 { A = 5.68E+04 n = 2.00 E = 25.94 }
1153    
1154     # From C2H2
1155     H39f: C4H4 + O -> C2H3 + HCCO { A = 3.70E+09 n = 1.28 E = 10.34 }
1156     # From C2H4 (x1/2)
1157     H40f: C4H4 + O -> C3H2 + CH2O { A = 3.58E+04 n = 2.47 E = 3.89 }
1158     H41f: C4H4 + O -> C3H3 + HCO { A = 1.95E+08 n = 1.36 E = 3.71 }
1159    
1160     H42f: C4H4 + OH -> CH2CO + C2H3 { A = 2.10E+01 n = 3.22 E = -1.76 }
1161     H43f: C4H4 + OH -> A-C3H5 + CO { A = 1.28E+09 n = 0.73 E = 10.79 }
1162    
1163    
1164     # Hexatriyne & Octotetrayne
1165     # -------------------------
1166    
1167     # Reactions of C6H2 & C8H2
1168     # Ceursters, Nguyen, Peeters, Nguyen 2000
1169     H44f: C4H2 + C2H -> C6H2 + H { A = 7.80E+13 n = .00 E = .00 }
1170     H45f: C2H2 + C4H -> C6H2 + H { A = 7.80E+13 n = .00 E = .00 }
1171     H46f: C6H2 + C2H -> C8H2 + H { A = 7.80E+13 n = .00 E = .00 }
1172     H47f: C4H2 + C4H -> C8H2 + H { A = 7.80E+13 n = .00 E = .00 }
1173    
1174     # Estimated
1175     H48f: C4H + C4H -> C8H2 { A = 1.00E+14 n = .00 E = .00 }
1176    
1177     # From C4H2 + OH
1178     H49 : C6H2 + OH -> C4H2 + HCCO { A = 3.41E+10 n = 0.31 E = 5.00 }
1179     H50 : C8H2 + OH -> C6H2 + HCCO { A = 3.41E+10 n = 0.31 E = 5.00 }
1180    
1181    
1182    
1183     #==========================================================================#
1184     # #
1185     # "Detailed kinetic modelling of butadiene Oxidation at high temperatures" #
1186     # A. Laskin, H. Wang, C. Law. #
1187     # Int. J. Chem. Kinet. 2000. 32-589 #
1188     # #
1189     #==========================================================================#
1190    
1191    
1192     # Butadiene
1193     # ---------
1194    
1195     # Baulch et al. 2005
1196     # Full rate to addition
1197     B01f: 2 C2H3 -> C4H6 { A = 8.43E+13 n = .00 E = .00 }
1198    
1199     # Ismail, Georgievskii, Taatjes, et al. 2007
1200     # Rates fitted at P=1.33bar
1201     B02f: C2H4 + C2H3 -> C4H6 + H { A = 2.15E+12 n = 0.46 E = 62.65 }
1202    
1203     B03f: C3H3 + CH3 + M9 -> C4H6 + M9 { A = 2.60E+57 n =-11.94 E = 40.89
1204     Ai= 1.50E+12 ni= .00 Ei= .00
1205     fcA = 0.825 fctA = 1340.6
1206     fcb = 0.175 fctb = 60000
1207     fcc = 1.0 fctc = 9769.8 }
1208    
1209     B04f: C3H6 + C2H3 -> C4H6 + CH3 { A = 7.23E+11 n = .00 E = 20.92 }
1210    
1211     # Lumping species 12-C4H6 into C4H6
1212     B05f: P-C3H4 + CH3 -> C4H6 + H { A = 8.94E+07 n = 1.14 E = 51.80 }
1213     B06f: A-C3H4 + CH3 -> C4H6 + H { A = 2.83E+08 n = 1.06 E = 46.70 }
1214    
1215     # Wang & Frenklach 1997
1216     B07f: C4H6 -> I-C4H5 + H { A = 5.70E+36 n = -6.27 E = 470.09 }
1217     B08f: C4H6 -> N-C4H5 + H { A = 5.30E+44 n = -8.62 E = 517.18 }
1218     B09f: C4H6 -> C4H4 + H2 { A = 2.50E+15 n = .00 E = 396.22 }
1219    
1220     # Adapted from C2H4 - 3kcal
1221     # Rate for OH from Vasu, Hanson, et al. 2010 - refitted
1222     B10f: C4H6 + H -> N-C4H5 + H2 { A = 1.27E+05 n = 2.75 E = 48.74 }
1223     B11f: C4H6 + H -> I-C4H5 + H2 { A = 6.35E+04 n = 2.75 E = 36.19 }
1224     B12f: C4H6 + OH -> N-C4H5 + H2O { A = 1.56E+05 n = 2.46 E = 7.78 }
1225     B13f: C4H6 + OH -> I-C4H5 + H2O { A = 2.17E+06 n = 2.08 E = 6.58 }
1226     B14f: C4H6 + CH3 -> N-C4H5 + CH4 { A = 2.06E-01 n = 3.94 E = 51.98 }
1227     B15f: C4H6 + CH3 -> I-C4H5 + CH4 { A = 1.03E-01 n = 3.94 E = 39.43 }
1228    
1229     B16f: C4H6 + C2H3 -> N-C4H5 + C2H4 { A = 5.00E+13 n = .00 E = 95.54 }
1230     B17f: C4H6 + C2H3 -> I-C4H5 + C2H4 { A = 2.50E+13 n = .00 E = 82.84 }
1231    
1232     # From C2H4 + O
1233     B18 : C4H6 + O -> A-C3H5 + CO + H { A = 7.66E+09 n = 0.88 E = 4.77 }
1234     B19f: C4H6 + O -> P-C3H4 + CH2O { A = 7.15E+04 n = 2.47 E = 3.89 }
1235     B20f: C4H6 + O -> A-C3H5 + HCO { A = 3.89E+08 n = 1.36 E = 3.71 }
1236    
1237    
1238     # Butadienyl radicals
1239     # -------------------
1240    
1241     # Wang & Frenklach 1994
1242     B21f: C2H3 + C2H2 -> N-C4H5 { A = 9.30E+38 n = -8.76 E = 50.21 }
1243    
1244     # Wang & Frenklach 1997
1245     B22f: 2 C2H3 -> I-C4H5 + H { A = 1.20E+22 n = -2.44 E = 57.13 }
1246     B23f: 2 C2H3 -> N-C4H5 + H { A = 2.40E+20 n = -2.04 E = 64.28 }
1247     B24f: 2 C2H3 -> C2H2 + C2H4 { A = 9.60E+11 n = .00 E = .00 }
1248    
1249     # Wang & Frenklach 1994
1250     B25f: C4H4 + H -> N-C4H5 { A = 1.30E+51 n =-11.92 E = 69.04 }
1251     B26f: C4H4 + H -> I-C4H5 { A = 4.90E+51 n =-11.92 E = 74.06 }
1252     B27f: N-C4H5 -> I-C4H5 { A = 1.50E+67 n =-16.89 E = 247.30 }
1253    
1254     # Wang & Frenklach 1997
1255     B28f: N-C4H5 + H -> I-C4H5 + H { A = 3.10E+26 n = -3.35 E = 72.90 }
1256    
1257     B29f: N-C4H5 + H -> C4H4 + H2 { A = 1.50E+13 n = .00 E = .00 }
1258     B30f: N-C4H5 + OH -> C4H4 + H2O { A = 2.50E+12 n = .00 E = .00 }
1259     B31f: N-C4H5 + HCO -> C4H6 + CO { A = 5.00E+12 n = .00 E = .00 }
1260     B32f: N-C4H5 + H2O2 -> C4H6 + HO2 { A = 1.21E+10 n = .00 E = -2.49 }
1261     B33f: N-C4H5 + HO2 -> C4H6 + O2 { A = 6.00E+11 n = .00 E = .00 }
1262    
1263     # From C2H3 + O
1264     B34f: N-C4H5 + O -> A-C3H5 + CO { A = 1.03E+13 n = 0.21 E = -1.79 }
1265    
1266     # From C2H3 + O2
1267     B35f: N-C4H5 + O2 -> C4H4 + HO2 { A = 6.70E+05 n = 1.61 E = -1.61 }
1268     B36 : N-C4H5 + O2 -> A-C3H5 + CO + O { A = 3.03E+11 n = 0.29 E = 0.05 }
1269     B37f: N-C4H5 + O2 -> HCO + C2H3CHO { A = 4.58E+16 n = -1.39 E = 4.25 }
1270    
1271     B38f: I-C4H5 + H -> C4H4 + H2 { A = 3.00E+13 n = .00 E = .00 }
1272     B39f: I-C4H5 + H -> C3H3 + CH3 { A = 2.00E+13 n = .00 E = 8.37 }
1273     B40f: I-C4H5 + OH -> C4H4 + H2O { A = 5.00E+12 n = .00 E = .00 }
1274     B41f: I-C4H5 + HCO -> C4H6 + CO { A = 5.00E+12 n = .00 E = .00 }
1275     B42f: I-C4H5 + HO2 -> C4H6 + O2 { A = 6.00E+11 n = .00 E = .00 }
1276     B43f: I-C4H5 + H2O2 -> C4H6 + HO2 { A = 1.21E+10 n = .00 E = -2.49 }
1277     B44f: I-C4H5 + O2 -> CH2CO + CH2CHO { A = 2.16E+10 n = .00 E = 10.46 }
1278    
1279     # From C2H5 + O
1280     B45f: I-C4H5 + O -> C3H3 + CH2O { A = 3.17E+13 n = 0.03 E = -1.65 }
1281    
1282     B46f: N-C4H5 + C2H3 -> A1-C6H6 + H2 { A = 1.84E-13 n = 7.07 E = -15.11 }
1283    
1284    
1285    
1286     #==========================================================================#
1287     # #
1288     # "A Detailed Chemical Kinetic Reaction Mechanism for #
1289     # n-Alkane Hydrocarbons from n-Octane to n-Hexadecane" #
1290     # C. K. Westbrook, W. J. Pitz, O. Herbinet, H. J. Curran and E. J. Silke #
1291     # Combustion and Flame 156:181-199 (2009). #
1292     # #
1293     # LLNL-MI-407455 - version dated 2008-09-02 C.K. Westbrook #
1294     # #
1295     #==========================================================================#
1296    
1297    
1298     # ------------------- HIGH TEMPERATURE -------------------- #
1299     # ---------------------- 3 Species ------------------------ #
1300     # --------------------- 17 Reactions ---------------------- #
1301    
1302     # Reactions of N-C6H14
1303    
1304     HX01 : N-C6H14 -> N-C5H11 + CH3 { A = 6.03E+18 n = -0.67 E = 362.13 }
1305     HX02 : N-C6H14 -> N-C4H9 + C2H5 { A = 1.62E+22 n = -1.49 E = 364.80 }
1306     HX03 : N-C6H14 -> N-C3H7 + N-C3H7 { A = 2.62e+22 n = -1.56 E = 367.94 }
1307    
1308     HX04 : N-C6H14 + H -> C6H13 + H2 { A = 6.16E+07 n = 2.10 E = 22.91 }
1309     HX05 : N-C6H14 + O -> C6H13 + OH { A = 1.42E+06 n = 2.56 E = 12.62 }
1310     HX06 : N-C6H14 + OH -> C6H13 + H2O { A = 7.49E+06 n = 2.09 E = -2.61 }
1311     HX07 : N-C6H14 + O2 -> C6H13 + HO2 { A = 1.70E+13 n = 0.20 E = 209.99 }
1312     HX08 : N-C6H14 + HO2 -> C6H13 + H2O2 { A = 6.27E+12 n = 0.21 E = 74.05 }
1313    
1314     # Reactions of C6H13 (lumped)
1315     # Branching ratios 0.2/0.4
1316    
1317     HX09 : C6H13 -> N-C4H9 + C2H4 { A = 3.20E+12 n = 0.13 E = 120.84 }
1318     HX10 : C6H13 -> N-C3H7 + C3H6 { A = 5.52E+12 n = 0.17 E = 125.16 }
1319     HX11 : C6H13 -> C2H5 + C4H8 { A = 2.76E+12 n = 0.17 E = 125.16 }
1320     HX12 : C6H13 -> CH3 + C5H10 { A = 2.76E+12 n = 0.17 E = 125.16 }
1321    
1322     HX13 : C6H13 -> C6H12 + H { A = 1.78E+08 n = 1.63 E = 144.24 }
1323    
1324     HX14 : C6H13 + HO2 -> C6H13O + OH { A = 7.00E+12 n = .00 E = -4.18 }
1325     HX15 : C6H13 + CH3O2 -> C6H13O + CH3O { A = 7.00E+12 n = .00 E = -4.18 }
1326    
1327     # Reactions of C6H13O
1328    
1329     HX16 : C6H13O -> N-C5H11 + CH2O { A = 1.19E+18 n = -1.50 E = 84.44 }
1330     HX17 : C6H13O -> N-C4H9 + CH3CHO { A = 7.16E+22 n = -2.78 E = 96.22 }
1331     HX18 : C6H13O -> N-C3H7 + C2H5 + HCO { A = 4.10E+17 n = -1.31 E = 81.60 }
1332    
1333    
1334    
1335     # ------------------- LOW TEMPERATURE -------------------- #
1336     # ---------------------- 5 Species ----------------------- #
1337     # -------------------- 11 Reactions ---------------------- #
1338    
1339     /* Commented for now
1340    
1341     # Formation of ROO
1342    
1343     HX20 : C6H13 + O2 -> C6H13O2 { A = 1.36E+13 n = -0.08 E = 0.87 }
1344     HX21 : C6H13O2 -> C6H13 + O2 { A = 1.71E+23 n = -2.33 E = 158.32 }
1345     HX22 : C6H13O2 -> C6H12OOH { A = 1.83E+05 n = 1.70 E = 80.90 }
1346    
1347     # Reactions of QOOH
1348    
1349     HX23 : C6H12OOH -> C6H13O2 { A = 7.53E+04 n = 1.25 E = 24.89 }
1350     HX24 : C6H12OOH -> C6H12 + HO2 { A = 4.01E+00 n = 3.28 E = 53.36 }
1351     HX25 : C6H12OOH -> C6H12O + OH { A = 1.33E+12 n = -0.74 E = 42.56 }
1352     HX26 : C6H12OOH + O2 -> C6H13O4 { A = 7.71E+12 n = -0.01 E = -0.06 }
1353    
1354     # Reactions of O2QOOH
1355    
1356     HX27 : C6H13O4 -> C6H12OOH + O2 { A = 2.31E+21 n = -1.97 E = 153.05 }
1357     HX28 : C6H13O4 -> OC6H11OOH + OH { A = 6.47E+09 n = 0.18 E = 83.01 }
1358    
1359     # Reactions of OQ'OOH
1360     # all products lumped
1361    
1362     HX29: OC6H11OOH -> C5H10 + CH2CO + OH { A = 3.26E+09 n = 1.93 E = 161.11 }
1363    
1364     # Reactions of QO
1365     # all products lumped
1366    
1367     HX30: C6H12O + OH -> N-C4H9 + CH2CO + H2O { A = 3.68E+12 n = .00 E = .00 }
1368     */
1369    
1370    
1371     #==========================================================================#
1372     # #
1373     # "A Comprehensive Modeling Study of n-Heptane Oxidation" #
1374     # Curran, H. J., Gaffuri, P., Pitz, W. J., and Westbrook, C. K. #
1375     # Combustion and Flame 114:149-177 (1998). #
1376     # #
1377     # UCRL-WEB-204236 - Review and release date: May 19, 2004. #
1378     # #
1379     #==========================================================================#
1380    
1381    
1382     # ------------------- HIGH TEMPERATURE -------------------- #
1383     # ---------------------- 3 Species ------------------------ #
1384     # --------------------- 19 Reactions ---------------------- #
1385    
1386     # Reactions of N-C7H16
1387    
1388     # Rates from LLNL
1389     # Multiplied by 3 to match overall decomp rate from exp
1390     # (Davidson, Oehlschlaeger, Hanson 2007)
1391     HP01 : N-C7H16 -> N-C6H13 + CH3 { A = 8.79E+73 n =-16.61 E = 497.48 }
1392     HP02 : N-C7H16 -> N-C5H11 + C2H5 { A = 2.43E+78 n =-17.62 E = 503.75 }
1393     HP03 : N-C7H16 -> N-C4H9 + N-C3H7 { A = 4.26E+78 n =-17.71 E = 505.01 }
1394    
1395     HP04 : N-C7H16 + H -> C7H15 + H2 { A = 9.90E+07 n = 2.06 E = 22.98 }
1396     HP05 : N-C7H16 + O -> C7H15 + OH { A = 1.72E+05 n = 2.81 E = 9.46 }
1397     HP06 : N-C7H16 + OH -> C7H15 + H2O { A = 9.68E+06 n = 2.08 E = -2.73 }
1398     HP07 : N-C7H16 + O2 -> C7H15 + HO2 { A = 2.89E+13 n = 0.20 E = 209.66 }
1399     HP08 : N-C7H16 + HO2 -> C7H15 + H2O2 { A = 7.57E+12 n = 0.21 E = 73.78 }
1400    
1401     # Reactions of C7H15 (lumped)
1402     # Branching ratios 0.17/0.33/0.17
1403     # NEW Branching ratios from OH rate about the same at 1000K
1404    
1405     HP09 : C7H15 -> N-C5H11 + C2H4 { A = 2.72E+12 n = 0.13 E = 120.84 }
1406     HP10 : C7H15 -> N-C4H9 + C3H6 { A = 4.55E+12 n = 0.17 E = 125.16 }
1407     HP11 : C7H15 -> N-C3H7 + C4H8 { A = 2.28E+12 n = 0.17 E = 125.16 }
1408     HP12 : C7H15 -> C2H5 + C5H10 { A = 2.35E+12 n = 0.17 E = 125.16 }
1409     HP13 : C7H15 -> CH3 + C6H12 { A = 2.28E+12 n = 0.17 E = 125.16 }
1410    
1411     HP14 : C7H15 -> C7H14 + H { A = 1.78E+08 n = 1.63 E = 144.24 }
1412    
1413     HP15 : C7H15 + HO2 -> C7H15O + OH { A = 7.00E+12 n = .00 E = -4.18 }
1414     HP16 : C7H15 + CH3O2 -> C7H15O + CH3O { A = 7.00E+12 n = .00 E = -4.18 }
1415    
1416     # Reactions of C7H15O (lumped)
1417    
1418     HP17 : C7H15O -> N-C5H11 + CH3CHO { A = 8.92E+19 n = -2.03 E = 87.88 }
1419     HP18 : C7H15O -> N-C4H9 + C2H5 + HCO { A = 2.23E+15 n = -0.70 E = 77.85 }
1420     HP19 : C7H15O -> N-C3H7 + N-C3H7 + HCO { A = 6.18E+16 n = -1.36 E = 77.48 }
1421    
1422    
1423     # ------------------- LOW TEMPERATURE -------------------- #
1424     # ---------------------- 5 Species ----------------------- #
1425     # -------------------- 11 Reactions ---------------------- #
1426    
1427 gblanqu 2.1 /* Commented for now */
1428 gblanqu 2.0
1429     # Formation of ROO
1430    
1431     HP20: C7H15 + O2 -> C7H15O2 { A = 1.68E+13 n = -0.11 E = 1.01 }
1432     HP21: C7H15O2 -> C7H15 + O2 { A = 1.92E+22 n = -2.11 E = 156.08 }
1433     HP22: C7H15O2 -> C7H14OOH { A = 1.88E+05 n = 1.68 E = 79.51 }
1434    
1435     # Reactions of QOOH
1436    
1437     HP23: C7H14OOH -> C7H15O2 { A = 7.64E+05 n = 0.91 E = 25.45 }
1438     HP24: C7H14OOH -> C7H14 + HO2 { A = 5.85E+03 n = 2.40 E = 64.08 }
1439     HP25: C7H14OOH -> C7H14O + OH { A = 3.97E-10 n = 5.69 E = 1.57 }
1440     HP26: C7H14OOH + O2 -> C7H15O4 { A = 1.51E+13 n = -0.09 E = 0.53 }
1441    
1442     # Reactions of O2QOOH
1443    
1444     HP27: C7H15O4 -> C7H14OOH + O2 { A = 1.71E+22 n = -2.13 E = 155.32 }
1445     HP28: C7H15O4 -> OC7H13OOH + OH { A = 4.25E+10 n = -0.11 E = 81.48 }
1446    
1447     # Reactions of OQ'OOH
1448     # all products lumped
1449    
1450     HP29: OC7H13OOH -> N-C3H7 + CH3CHO + CH2CO + OH { A = 3.26E+09 n = 1.93 E = 161.11 }
1451    
1452     # Reactions of QO
1453     # all products lumped
1454    
1455 gblanqu 2.1 HP30: C7H14O + OH -> N-C5H11 + CH2CO + H2O { A = 3.68E+12 n = .00 E = .00 }
1456     /**/
1457 gblanqu 2.0
1458    
1459    
1460     #==========================================================================#
1461     # #
1462     # "A Detailed Chemical Kinetic Reaction Mechanism for #
1463     # n-Alkane Hydrocarbons from n-Octane to n-Hexadecane" #
1464     # C. K. Westbrook, W. J. Pitz, O. Herbinet, H. J. Curran and E. J. Silke #
1465     # Combustion and Flame 156:181-199 (2009). #
1466     # #
1467     # LLNL-MI-407455 - version dated 2008-09-02 C.K. Westbrook #
1468     # #
1469     #==========================================================================#
1470    
1471     # H-abs by H from Cartensen & Dean 2009
1472     # H-abs by OH from Kwok & Atkinson 1995 / Pang, Hanson et al. 2011
1473     # Total decomp rate fitted to McDonald 2012 and Klingbeil et al. 2008
1474     # -> individual rates rescaled with same branching ratios
1475    
1476     # ------------------- HIGH TEMPERATURE -------------------- #
1477     # ---------------------- 3 Species ------------------------ #
1478     # --------------------- 73 Reactions ---------------------- #
1479    
1480     # Reactions of N-C12H26
1481    
1482     DD01 : N-C12H26 -> N-C10H21 + C2H5 { A = 1.68E+24 n = -2.11 E = 368.84 }
1483     DD02 : N-C12H26 -> N-C9H19 + N-C3H7 { A = 2.46E+24 n = -2.12 E = 371.27 }
1484     DD03 : N-C12H26 -> N-C8H17 + N-C4H9 { A = 1.21E+24 n = -2.07 E = 369.64 }
1485     DD04 : N-C12H26 -> N-C7H15 + N-C5H11 { A = 1.13E+24 n = -2.06 E = 369.58 }
1486     DD05 : N-C12H26 -> N-C6H13 + N-C6H13 { A = 2.59E+24 n = -2.12 E = 369.69 }
1487    
1488     DD06 : N-C12H26 + H -> C12H25 + H2 { A = 3.59E+08 n = 1.97 E = 23.16 }
1489     DD07 : N-C12H26 + O -> C12H25 + OH { A = 3.97E+05 n = 2.76 E = 9.19 }
1490     DD08 : N-C12H26 + OH -> C12H25 + H2O { A = 2.18E+07 n = 2.05 E = -2.95 }
1491     DD09 : N-C12H26 + O2 -> C12H25 + HO2 { A = 1.05E+14 n = 0.10 E = 209.77 }
1492     DD10 : N-C12H26 + HO2 -> C12H25 + H2O2 { A = 2.86E+13 n = 0.11 E = 73.93 }
1493    
1494     # Reactions of C12H25 (lumped)
1495     # Branching ratios 0.09/.18
1496     # NEW Branching ratios from OH rate about same at 1000K
1497    
1498     DD11 : C12H25 -> N-C10H21 + C2H4 { A = 1.44E+12 n = 0.13 E = 120.84 }
1499     DD12 : C12H25 -> N-C9H19 + C3H6 { A = 2.48E+12 n = 0.17 E = 125.16 }
1500     DD13 : C12H25 -> N-C8H17 + C4H8 { A = 2.48E+12 n = 0.17 E = 125.16 }
1501     DD14 : C12H25 -> N-C7H15 + C5H10 { A = 1.24E+12 n = 0.17 E = 125.16 }
1502     DD15 : C12H25 -> N-C6H13 + C6H12 { A = 1.24E+12 n = 0.17 E = 125.16 }
1503     DD16 : C12H25 -> N-C5H11 + C7H14 { A = 1.24E+13 n = 0.17 E = 125.16 }
1504     DD17 : C12H25 -> N-C4H9 + C8H16 { A = 1.24E+13 n = 0.17 E = 125.16 }
1505     DD18 : C12H25 -> N-C3H7 + C9H18 { A = 1.24E+12 n = 0.17 E = 125.16 }
1506     DD19 : C12H25 -> C2H5 + C10H20 { A = 1.24E+12 n = 0.17 E = 125.16 }
1507    
1508     DD20 : C12H25 -> C12H24 + H { A = 1.78E+08 n = 1.63 E = 144.24 }
1509    
1510     DD21 : C12H25 + HO2 -> C12H25O + OH { A = 7.00E+12 n = .00 E = -4.18 }
1511     DD22 : C12H25 + CH3O2 -> C12H25O + CH3O { A = 7.00E+12 n = .00 E = -4.18 }
1512    
1513     # Reactions of C12H25O
1514    
1515     DD23 : C12H25O -> N-C10H21 + CH3CHO { A = 4.35E+08 n = 1.31 E = 64.79 }
1516     DD24 : C12H25O -> N-C9H19 + C2H5 + HCO { A = 8.37E+18 n = -1.84 E = 82.98 }
1517     DD25 : C12H25O -> N-C8H17 + N-C3H7 + HCO { A = 9.83E+44 n = -9.70 E = 134.38 }
1518     DD26 : C12H25O -> N-C7H15 + N-C4H9 + HCO { A = 8.35E+61 n =-14.50 E = 179.77 }
1519     DD27 : C12H25O -> N-C6H13 + N-C5H11 + HCO { A = 4.63E+64 n =-15.38 E = 182.82 }
1520    
1521     # Reactions of C12H24 (lumped)
1522    
1523     DD28 : C12H24 -> N-C9H19 + A-C3H5 { A = 9.53E+15 n = -0.18 E = 298.01 }
1524     DD32 : C12H24 -> N-C8H17 + C4H7 { A = 1.87E+15 n = 0.04 E = 296.85 }
1525     DD31 : C12H24 -> N-C7H15 + C5H9 { A = 1.50E+15 n = -0.02 E = 297.10 }
1526     DD30 : C12H24 -> N-C5H11 + C7H13 { A = 2.08E+15 n = -0.04 E = 297.23 }
1527     DD29 : C12H24 -> N-C4H9 + C8H15 { A = 1.51E+13 n = 0.52 E = 294.52 }
1528    
1529     DD33 : C12H24 + H -> C12H23 + H2 { A = 3.70E+13 n = .00 E = 16.32 }
1530     DD34 : C12H24 + OH -> C12H23 + H2O { A = 3.00E+13 n = .00 E = 5.15 }
1531    
1532     # Reactions of C12H23 (lumped)
1533    
1534     DD35 : C12H23 -> C10H19 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1535     DD36 : C12H23 -> C9H17 + C3H6 { A = 1.38E+13 n = 0.17 E = 125.16 }
1536     DD37 : C12H23 -> C8H15 + C4H8 { A = 1.38E+13 n = 0.17 E = 125.16 }
1537     DD38 : C12H23 -> C7H13 + C5H10 { A = 1.38E+13 n = 0.17 E = 125.16 }
1538     DD39 : C12H23 -> C5H9 + C7H14 { A = 1.38E+13 n = 0.17 E = 125.16 }
1539     DD40 : C12H23 -> C4H7 + C8H16 { A = 1.38E+13 n = 0.17 E = 125.16 }
1540     DD41 : C12H23 -> A-C3H5 + C9H18 { A = 1.38E+13 n = 0.17 E = 125.16 }
1541     DD42 : C12H23 -> C2H3 + C10H20 { A = 1.38E+13 n = 0.17 E = 125.16 }
1542    
1543    
1544    
1545    
1546     # -------------------- LOW TEMPERATURE -------------------- #
1547     # ----------------------- 10 Species ---------------------- #
1548     # ---------------------- 21 Reactions --------------------- #
1549     /*
1550     # Reactions of C12H25O2
1551     # Backward rate reduced (x1/6)
1552     # to mimic lumping of peroxy species
1553    
1554     DD50 : C12H25 + O2 -> C12H25O2 { A = 9.52E+12 n = -0.04 E = 0.23 }
1555     DD51 : C12H25O2 -> C12H25 + O2 { A = 1.52E+22 n = -2.31 E = 156.59 }
1556     DD52 : C12H25O2 -> C12H24OOH { A = 1.13E+06 n = 1.46 E = 80.17 }
1557     DD53 : C12H24OOH -> C12H25O2 { A = 4.47E+21 n = -3.86 E = 58.11 }
1558    
1559     # Reactions of C12H24OOH
1560    
1561     DD54 : C12H24OOH -> C12H24 + HO2 { A = 2.21E+14 n = -0.81 E = 84.74 }
1562     DD55 : C12H24OOH -> C12H24O + OH { A = 3.25E-11 n = 5.92 E = -7.84 }
1563     DD56 : C12H24OOH + O2 -> C12H25O4 { A = 1.32E+13 n = -0.08 E = 0.47 }
1564    
1565     # Reactions of C12H25O4
1566    
1567     DD57 : C12H25O4 -> C12H24OOH + O2 { A = 1.92E+23 n = -2.42 E = 157.60 }
1568     DD58 : C12H25O4 -> C12H24O3 + OH { A = 1.28E+07 n = 0.89 E = 72.18 }
1569    
1570     # Reactions of C12H24O3
1571     # lump all decomposition pathways
1572    
1573     DD59 : C12H24O3 -> N-C8H17 + CH3CHO + CH2CO + OH{ A = 8.95E+14 n = 0.32 E = 171.10 }
1574    
1575     # Reactions of C12H24O
1576     # lump all decomposition pathways
1577    
1578     DD60 : C12H24O + OH -> N-C8H17 + C2H4 + CH2CO + H2O{ A = 3.09E+13 n = -0.27 E = 1.61 }
1579    
1580     # Reactions of C8H17O2
1581    
1582     DD61 : N-C8H17 + O2 -> C8H17O2 { A = 1.65E+22 n = -2.85 E = 19.78 }
1583     DD62 : C8H17O2 -> N-C8H17 + O2 { A = 2.48E+21 n = -1.94 E = 150.73 }
1584     DD63 : C8H17O2 -> C8H16OOH { A = 1.11E+06 n = 1.40 E = 79.77 }
1585    
1586     # Reactions of C8H16OOH
1587    
1588     DD64 : C8H16OOH -> C8H16O + OH { A = 3.07E+02 n = 2.15 E = 24.57 }
1589     DD65 : C8H16OOH -> C8H16 + HO2 { A = 5.11E+06 n = 1.40 E = 70.08 }
1590     DD66 : C8H16OOH + O2 -> C8H17O4 { A = 1.16E+11 n = 0.53 E = -3.58 }
1591    
1592     # Reactions of C8H17O4/C8H16O3
1593    
1594     DD67 : C8H17O4 -> C8H16OOH + O2 { A = 1.37E+23 n = -2.37 E = 157.49 }
1595     DD68 : C8H17O4 -> C8H16O3 + OH { A = 9.98E+06 n = 1.02 E = 83.92 }
1596     DD69 : C8H16O3 -> N-C4H9 + CH3CHO + CH2CO + OH { A = 4.44E+32 n = -4.98 E = 207.98 }
1597    
1598     DD70 : C8H16O + OH -> N-C6H13 + CH2CO + H2O { A = 3.09E+13 n = -0.27 E = 1.61 }
1599     */
1600    
1601    
1602    
1603     #==========================================================================#
1604     # #
1605     # Additional n-alkyl mechanism #
1606     # (based on) #
1607     # Lawrence Livermore n-Alkanes Mechanism - ver 2 #
1608     # #
1609     #==========================================================================#
1610    
1611    
1612     # ------------------- HIGH TEMPERATURE -------------------- #
1613     # ---------------------- 21 Species ----------------------- #
1614     # --------------------- 70 Reactions ---------------------- #
1615    
1616     # H-abstractions from Miller & Klippenstein 2013 - HPL
1617     # p -> { A = 1.78E+08 n = 1.63 E = 144.24 }
1618     # Beta scissions from Ratkiewicz & Truong 2012 - HPL
1619     # p -> { A = 1.60E+13 n = 0.13 E = 120.84 }
1620     # st -> { A = 1.38E+13 n = 0.17 E = 125.16 }
1621     # H-abstraction for alkane from Cartensen & Dean 2009
1622     # p -> { A = 1.40E+07 n = 1.97 E = 34.31 }
1623     # s -> { A = 3.80E+07 n = 1.86 E = 23.43 }
1624    
1625    
1626     # Decyl radical
1627     # -------------
1628    
1629     # Reactions of N-C10H21
1630    
1631     NC01 : N-C10H21 -> N-C8H17 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1632     NC02 : N-C10H21 -> C10H20 + H { A = 2.04E+10 n = 0.95 E = 141.45 }
1633    
1634     # Reactions of C10H20
1635    
1636     NC03 : C10H20 -> N-C7H15 + A-C3H5 { A = 1.00E+16 n = .00 E = 297.06 }
1637    
1638     NC04 : C10H20 + H -> C10H19 + H2 { A = 3.70E+13 n = .00 E = 16.32 }
1639     NC05 : C10H20 + OH -> C10H19 + H2O { A = 3.00E+13 n = .00 E = 5.15 }
1640    
1641     # Reactions of C10H19 (lumped)
1642    
1643     NC06 : C10H19 -> C8H15 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1644     NC07 : C10H19 -> C7H13 + C3H6 { A = 1.38E+13 n = 0.17 E = 125.16 }
1645     NC08 : C10H19 -> C6H11 + C4H8 { A = 1.38E+13 n = 0.17 E = 125.16 }
1646     NC09 : C10H19 -> C5H9 + C5H10 { A = 1.38E+13 n = 0.17 E = 125.16 }
1647     NC10 : C10H19 -> C4H7 + C6H12 { A = 1.38E+13 n = 0.17 E = 125.16 }
1648     NC11 : C10H19 -> A-C3H5 + C7H14 { A = 1.38E+13 n = 0.17 E = 125.16 }
1649     NC12 : C10H19 -> C2H3 + C8H16 { A = 1.38E+13 n = 0.17 E = 125.16 }
1650    
1651    
1652     # Nonyl radical
1653     # -------------
1654    
1655     # Reactions of N-C9H19
1656    
1657     NC13 : N-C9H19 -> N-C7H15 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1658     NC14 : N-C9H19 -> C9H18 + H { A = 2.04E+10 n = 0.95 E = 141.45 }
1659    
1660     # Reactions of C9H18
1661    
1662     NC15 : C9H18 -> N-C6H13 + A-C3H5 { A = 1.00E+16 n = .00 E = 297.06 }
1663    
1664     NC16 : C9H18 + H -> C9H17 + H2 { A = 3.70E+13 n = .00 E = 16.32 }
1665     NC17 : C9H18 + OH -> C9H17 + H2O { A = 3.00E+13 n = .00 E = 5.15 }
1666    
1667     # Reactions of C9H17 (lumped)
1668    
1669     NC18 : C9H17 -> C7H13 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1670     NC19 : C9H17 -> C6H11 + C3H6 { A = 1.38E+13 n = 0.17 E = 125.16 }
1671     NC20 : C9H17 -> C5H9 + C4H8 { A = 1.38E+13 n = 0.17 E = 125.16 }
1672     NC21 : C9H17 -> C4H7 + C5H10 { A = 1.38E+13 n = 0.17 E = 125.16 }
1673     NC22 : C9H17 -> A-C3H5 + C6H12 { A = 1.38E+13 n = 0.17 E = 125.16 }
1674     NC23 : C9H17 -> C2H3 + C7H14 { A = 1.38E+13 n = 0.17 E = 125.16 }
1675    
1676    
1677     # Octyl radical
1678     # -------------
1679    
1680     # Reactions of N-C8H17
1681    
1682     NC24 : N-C8H17 -> N-C6H13 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1683     NC25 : N-C8H17 -> C8H16 + H { A = 2.04E+10 n = 0.95 E = 141.45 }
1684    
1685     # Reactions of C8H16
1686    
1687     NC26 : C8H16 -> N-C5H11 + A-C3H5 { A = 1.00E+16 n = .00 E = 297.06 }
1688    
1689     NC27 : C8H16 + H -> C8H15 + H2 { A = 3.70E+13 n = .00 E = 16.32 }
1690     NC28 : C8H16 + OH -> C8H15 + H2O { A = 3.00E+13 n = .00 E = 5.15 }
1691    
1692     # Reactions of C8H15 (lumped)
1693    
1694     NC29 : C8H15 -> C6H11 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1695     NC30 : C8H15 -> C5H9 + C3H6 { A = 1.38E+13 n = 0.17 E = 125.16 }
1696     NC31 : C8H15 -> C4H7 + C4H8 { A = 1.38E+13 n = 0.17 E = 125.16 }
1697     NC32 : C8H15 -> A-C3H5 + C5H10 { A = 1.38E+13 n = 0.17 E = 125.16 }
1698     NC33 : C8H15 -> C2H3 + C6H12 { A = 1.38E+13 n = 0.17 E = 125.16 }
1699    
1700    
1701     # Heptyl radical
1702     # --------------
1703    
1704     # Reactions of N-C7H15
1705    
1706     NC34 : N-C7H15 -> N-C5H11 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1707     NC35 : N-C7H15 -> C7H14 + H { A = 2.04E+10 n = 0.95 E = 141.45 }
1708    
1709     # Reactions of C7H14
1710    
1711     NC36 : C7H14 -> N-C4H9 + A-C3H5 { A = 1.00E+16 n = .00 E = 297.06 }
1712    
1713     NC37 : C7H14 + H -> C7H13 + H2 { A = 3.70E+13 n = .00 E = 16.32 }
1714     NC38 : C7H14 + OH -> C7H13 + H2O { A = 3.00E+13 n = .00 E = 5.15 }
1715    
1716     # Reactions of C7H13 (lumped)
1717    
1718     NC39 : C7H13 -> C5H9 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1719     NC40 : C7H13 -> C4H7 + C3H6 { A = 1.38E+13 n = 0.17 E = 125.16 }
1720     NC41 : C7H13 -> A-C3H5 + C4H8 { A = 1.38E+13 n = 0.17 E = 125.16 }
1721     NC42 : C7H13 -> C2H3 + C5H10 { A = 1.38E+13 n = 0.17 E = 125.16 }
1722    
1723    
1724     # Hexyl radical
1725     # -------------
1726    
1727     # Reactions of N-C6H13
1728    
1729     NC43 : N-C6H13 -> N-C4H9 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1730     NC44 : N-C6H13 -> C6H12 + H { A = 2.04E+10 n = 0.95 E = 141.45 }
1731    
1732     # Reactions of C6H12
1733    
1734     NC45 : C6H12 -> N-C3H7 + A-C3H5 { A = 8.52E+26 n = -3.39 E = 320.10 }
1735    
1736     NC46 : C6H12 + H -> C6H11 + H2 { A = 3.70E+13 n = .00 E = 16.32 }
1737     NC47 : C6H12 + OH -> C6H11 + H2O { A = 3.00E+13 n = .00 E = 5.15 }
1738    
1739     # Reactions of C6H11 (lumped)
1740    
1741     NC48 : C6H11 -> C4H7 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1742     NC49 : C6H11 -> A-C3H5 + C3H6 { A = 1.38E+13 n = 0.17 E = 125.16 }
1743     NC50 : C6H11 -> C2H3 + C4H8 { A = 1.38E+13 n = 0.17 E = 125.16 }
1744    
1745    
1746     # Pentyl radical
1747     # --------------
1748    
1749     # Reactions of N-C5H11
1750    
1751     NC51 : N-C5H11 -> N-C3H7 + C2H4 { A = 3.24E+12 n = 0.32 E = 120.53 }
1752     NC52 : N-C5H11 -> C3H6 + C2H5 { A = 1.15E+01 n = 3.03 E = 64.07 }
1753     NC53 : N-C5H11 -> C5H10 + H { A = 2.04E+10 n = 0.95 E = 141.45 }
1754    
1755     # Reactions of C5H10
1756    
1757     NC54 : C5H10 -> A-C3H5 + C2H5 { A = 1.00E+16 n = .00 E = 297.06 }
1758    
1759     NC55 : C5H10 + H -> C5H9 + H2 { A = 3.70E+13 n = .00 E = 16.32 }
1760     NC56 : C5H10 + OH -> C5H9 + H2O { A = 3.00E+13 n = .00 E = 5.15 }
1761    
1762     # Reactions of C5H9 (lumped)
1763    
1764     NC57 : C5H9 -> A-C3H5 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1765     NC58 : C5H9 -> C2H3 + C3H6 { A = 1.38E+13 n = 0.17 E = 125.16 }
1766    
1767    
1768     # Butyl radical
1769     # -------------
1770    
1771     # Reactions of N-C4H9
1772    
1773     NC59 : N-C4H9 -> C2H5 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 }
1774     NC60 : N-C4H9 -> C4H8 + H { A = 2.04E+10 n = 0.95 E = 141.45 }
1775    
1776     # Reactions of C4H8 reactions
1777    
1778     NC61 : C4H8 -> A-C3H5 + CH3 { A = 1.00E+16 n = .00 E = 297.06 }
1779    
1780     NC62 : C4H8 + H -> C4H7 + H2 { A = 3.70E+13 n = .00 E = 16.32 }
1781     NC63 : C4H8 + OH -> C4H7 + H2O { A = 3.00E+13 n = .00 E = 5.15 }
1782    
1783     # Reactions of C4H7
1784    
1785     NC64 : C4H7 -> C2H4 + C2H3 { A = 1.00E+11 n = .00 E = 154.81 }
1786     NC65 : C4H7 -> C4H6 + H { A = 1.20E+14 n = .00 E = 206.27 }
1787    
1788     NC66 : C4H7 + H -> C4H6 + H2 { A = 3.16E+13 n = .00 E = .00 }
1789     NC67 : C4H7 + O2 -> C4H6 + HO2 { A = 1.00E+09 n = .00 E = .00 }
1790     NC68 : C4H7 + CH3 -> C4H6 + CH4 { A = 8.00E+12 n = .00 E = .00 }
1791    
1792     NC69 : C4H7 + HO2 -> A-C3H5 + CH2O + OH { A = 7.00E+12 n = .00 E = -4.18 }
1793     NC70 : C4H7 + CH3O2 -> A-C3H5 + CH2O + CH3O { A = 7.00E+12 n = .00 E = -4.18 }
1794    
1795    
1796    
1797    
1798     #==========================================================================#
1799     # #
1800     # M. Mehl, H. J. Curran, W. J. Pitz, and C. K. Westbrook, 2009 #
1801     # LLNL-MI-421507 - Review and release date: December 16, 2009 #
1802     # #
1803     #==========================================================================#
1804    
1805    
1806     # ------------------- HIGH TEMPERATURE -------------------- #
1807     # ---------------------- 15 Species ----------------------- #
1808     # --------------------- 73 Reactions ---------------------- #
1809    
1810     # Reactions of I-C8H18
1811    
1812     IC00 : I-C8H18 -> Y-C7H15 + CH3 { A = 6.18E+25 n = -2.46 E = 350.24 }
1813     IC01 : I-C8H18 -> T-C4H8 + I-C3H7 + CH3 { A = 2.46E+23 n = -2.01 E = 348.95 }
1814     IC02 : I-C8H18 -> 2 T-C4H9 { A = 7.83E+29 n = -3.93 E = 352.08 }
1815    
1816     IC03 : I-C8H18 + H -> C-C8H17 + H2 { A = 9.08E+00 n = 4.12 E = 7.45 }
1817     IC04 : I-C8H18 + O -> C-C8H17 + OH { A = 4.69E+03 n = 3.19 E = 4.52 }
1818     IC05 : I-C8H18 + OH -> C-C8H17 + H2O { A = 2.70E+05 n = 2.43 E = -4.04 }
1819     IC06 : I-C8H18 + O2 -> C-C8H17 + HO2 { A = 1.03E+11 n = 0.84 E = 196.29 }
1820     IC07 : I-C8H18 + CH3 -> C-C8H17 + CH4 { A = 1.14E-18 n = 9.25 E = -8.89 }
1821     IC08 : I-C8H18 + HO2 -> C-C8H17 + H2O2 { A = 9.85E+10 n = 0.73 E = 70.89 }
1822     IC09 : I-C8H18 + CH3O2 -> C-C8H17 + CH3O + OH { A = 9.85E+10 n = 0.73 E = 70.89 }
1823    
1824     # Reactions of C-C8H17
1825    
1826     IC10 : C-C8H17 -> Y-C7H14 + CH3 { A = 2.55E+39 n = -7.47 E = 189.48 }
1827     IC11 : C-C8H17 -> T-C4H9 + T-C4H8 { A = 4.28E+22 n = -2.81 E = 127.70 }
1828     IC12 : C-C8H17 -> T-C4H8 + CH3 + C3H6 { A = 4.22E+24 n = -3.34 E = 158.66 }
1829    
1830     IC13 : C-C8H17 + HO2 -> D-C8H17O + OH { A = 7.00E+12 n = .00 E = -4.18 }
1831     IC14 : C-C8H17 + CH3O2 -> D-C8H17O + CH3O { A = 7.00E+12 n = .00 E = -4.18 }
1832    
1833     # Reactions of D-C8H17O
1834    
1835     IC15 : D-C8H17O -> T-C4H8 + CH3 + CH3COCH3 { A = 1.33E+23 n = -2.98 E = 64.44 }
1836     IC16 : D-C8H17O -> T-C4H9 + I-C3H7 + HCO { A = 7.95E+33 n = -6.00 E = 97.57 }
1837     IC17 : D-C8H17O -> Y-C7H15 + CH2O { A = 2.69E+20 n = -2.08 E = 62.99 }
1838    
1839     # Reactions of Y-C7H15
1840    
1841     IC18 : Y-C7H15 -> T-C4H9 + C3H6 { A = 5.14E+23 n = -2.93 E = 131.78 }
1842     IC19 : Y-C7H15 -> T-C4H8 + I-C3H7 { A = 5.87E+21 n = -2.57 E = 136.80 }
1843     IC20 : Y-C7H15 -> Y-C7H14 + H { A = 6.13E+13 n = 0.03 E = 153.44 }
1844    
1845     # Reactions of Y-C7H14
1846    
1847     IC21 : Y-C7H14 -> T-C4H9 + A-C3H5 { A = 3.98E+26 n = -3.48 E = 320.14 }
1848     IC22 : Y-C7H14 -> T-C4H7 + I-C3H7 { A = 5.29E+24 n = -2.55 E = 317.38 }
1849    
1850     IC23 : Y-C7H14 + H -> X-C7H13 + H2 { A = 2.38E-13 n = 7.67 E = -47.65 }
1851     IC24 : Y-C7H14 + OH -> X-C7H13 + H2O { A = 7.76E-09 n = 6.18 E = -41.33 }
1852    
1853     # Reactions of X-C7H13
1854    
1855     IC25 : X-C7H13 -> T-C4H9 + A-C3H4 { A = 8.71E+21 n = -2.43 E = 249.07 }
1856     IC26 : X-C7H13 -> T-C4H8 + T-C3H5 { A = 6.32E+18 n = -1.80 E = 182.42 }
1857     IC27 : X-C7H13 -> T-C4H7 + C3H6 { A = 2.10E+16 n = -1.09 E = 74.56 }
1858    
1859     #C28 : X-C7H13 + HO2 -> I-C3H5CHO + I-C3H7 + OH { A = 1.00E+13 n = .00 E = .00 }
1860    
1861     # Reactions of T-C4H9
1862    
1863     # Ratkeiwicz 2011 (x0.5 for lumping)
1864     IC29 : T-C4H9 -> C3H6 + CH3 { A = 3.30E+12 n = 0.37 E = 128.58 }
1865    
1866     IC30 : T-C4H9 -> T-C4H8 + H { A = 5.35E+10 n = 1.06 E = 137.99 }
1867    
1868     #C31 : T-C4H9 + HO2 -> T-C4H9O + OH { A = 7.00E+12 n = .00 E = -4.18 }
1869     #C32 : T-C4H9 + CH3O2 -> T-C4H9O + CH3O { A = 7.00E+12 n = .00 E = -4.18 }
1870    
1871     # Reactions of T-C4H9O
1872    
1873     #C33 : T-C4H9O -> I-C3H7 + HCO + H { A = 1.78E+39 n = -7.30 E = 156.05 }
1874     #C34 : T-C4H9O -> I-C3H7 + CH2O { A = 7.25E+39 n = -7.59 E = 140.03 }
1875     #C35 : T-C4H9O -> CH3COCH3 + CH3 { A = 3.09E+13 n = 0.03 E = 58.87 }
1876    
1877     # Reactions of T-C4H8
1878     # (not lumped)
1879    
1880     IC36 : T-C4H8 -> T-C3H5 + CH3 { A = 1.92E+66 n =-14.22 E = 535.97 }
1881     IC37 : T-C4H8 + H -> C3H6 + CH3 { A = 5.68E+33 n = -5.72 E = 83.68 }
1882    
1883     IC38 : T-C4H8 + H -> T-C4H7 + H2 { A = 3.40E+05 n = 2.50 E = 10.43 }
1884     IC39 : T-C4H8 + O -> T-C4H7 + OH { A = 1.21E+11 n = 0.70 E = 31.94 }
1885     IC40 : T-C4H8 + OH -> T-C4H7 + H2O { A = 5.20E+06 n = 2.00 E = -1.25 }
1886     IC41 : T-C4H8 + CH3 -> T-C4H7 + CH4 { A = 4.42E+00 n = 3.50 E = 23.74 }
1887     IC42 : T-C4H8 + HO2 -> T-C4H7 + H2O2 { A = 1.93E+04 n = 2.60 E = 58.20 }
1888    
1889     #C43 : T-C4H8 + O -> I-C3H7 + HCO { A = 1.58E+07 n = 1.76 E = -5.09 }
1890     #C44 : T-C4H8 + O -> CH2CO + 2 CH3 { A = 3.33E+07 n = 1.76 E = 0.32 }
1891    
1892     # Reactions of T-C4H7
1893     # (not lumped)
1894    
1895     IC45 : T-C4H7 -> A-C3H4 + CH3 { A = 1.23E+47 n = -9.74 E = 310.70 }
1896    
1897     #C46 : T-C4H7 + O -> I-C3H5CHO + H { A = 6.03E+13 n = .00 E = .00 }
1898     #C47 : T-C4H7 + O2 -> I-C3H5CHO + OH { A = 2.47E+13 n = -0.45 E = 96.32 }
1899     #C48 : T-C4H7 + O2 -> CH2CO + CH2O + CH3 { A = 7.14E+15 n = -1.21 E = 88.07 }
1900     #C49 : T-C4H7 + O2 -> A-C3H4 + CH2O + OH { A = 7.29E+29 n = -5.71 E = 89.75 }
1901     #C50 : T-C4H7 + HO2 -> T-C4H7O + OH { A = 7.00E+12 n = .00 E = -4.18 }
1902    
1903     # Reactions of T-C4H7O
1904     # (not lumped)
1905    
1906     #C51 : T-C4H7O -> I-C3H5CHO + H { A = 5.00E+13 n = .00 E = 121.75 }
1907     #C52 : T-C4H7O -> T-C3H5 + CH2O { A = 2.93E+21 n = -2.39 E = 148.91 }
1908     #C53 : T-C4H7O + O2 -> I-C3H5CHO + HO2 { A = 3.00E+10 n = .00 E = 6.90 }
1909    
1910     # Reactions of I-C3H5CHO
1911     # (not lumped)
1912    
1913     #C54 : I-C3H5CHO -> T-C3H5 + HCO { A = 3.05E+23 n = -2.37 E = 415.22 }
1914    
1915     #C55 : I-C3H5CHO + H -> T-C3H5 + CO + H2 { A = 2.60E+12 n = .00 E = 10.88 }
1916     #C56 : I-C3H5CHO + O -> T-C3H5 + CO + OH { A = 7.18E+12 n = .00 E = 5.81 }
1917     #C57 : I-C3H5CHO + OH -> T-C3H5 + CO + H2O { A = 2.69E+10 n = 0.76 E = -1.42 }
1918     #C58 : I-C3H5CHO + CH3 -> T-C3H5 + CO + CH4 { A = 3.98E+12 n = .00 E = 36.40 }
1919     #C59 : I-C3H5CHO + HO2 -> T-C3H5 + CO + H2O2 { A = 1.00E+12 n = .00 E = 49.87 }
1920    
1921     # Reactions of CH3COCH3
1922     # Revised from LLNL-NC16
1923     # (not lumped)
1924    
1925     IC60 : CH3COCH3 -> 2 CH3 + CO { A = 1.22E+23 n = -1.99 E = 351.25 }
1926    
1927     IC61 : CH3COCH3 + H -> CH2CO + CH3 + H2 { A = 2.30E+05 n = 2.72 E = 26.19 }
1928     IC62 : CH3COCH3 + O -> CH2CO + CH3 + OH { A = 5.13E+11 n = 0.21 E = 20.46 }
1929     IC63 : CH3COCH3 + OH -> CH2CO + CH3 + H2O { A = 3.38E+07 n = 1.74 E = 3.47 }
1930     IC64 : CH3COCH3 + O2 -> CH2CO + CH3 + HO2 { A = 6.03E+13 n = .00 E = 202.92 }
1931     IC65 : CH3COCH3 + CH3 -> CH2CO + CH3 + CH4 { A = 3.96E+11 n = .00 E = 40.94 }
1932     IC66 : CH3COCH3 + HO2 -> CH2CO + CH3 + H2O2 { A = 1.70E+13 n = .00 E = 85.61 }
1933    
1934    
1935    
1936     #==========================================================================#
1937     # #
1938     # Zhong & Bozzelli, Int. J. Chem. Kinet., 1997, 29, 893-913 #
1939     # Zhong & Bozzelli, J. Phys. Chem. A, 1998, 102, 3537-3555 #
1940     # Robinson & Lindstedt, Comb. Flame, 2011, 158, 666-686 #
1941     # #
1942     #==========================================================================#
1943    
1944    
1945     # Cyclopentadiene
1946     # ---------------
1947    
1948     # Robinson & Lindstedt 2011
1949     CP01f: C5H6 -> C5H5 + H { A = 3.24E+49 n =-10.01 E = 423.40 }
1950     CP02f: C5H6 + H -> C5H5 + H2 { A = 8.59E+07 n = 1.85 E = 13.97 }
1951    
1952     CP03f: C5H6 + H -> A-C3H5 + C2H2 { A = 7.74E+36 n = -6.81 E = 137.60 }
1953    
1954     CP04f: C5H6 + O -> C5H5 + OH { A = 4.77E+04 n = 2.71 E = 4.63 }
1955     CP05f: C5H6 + OH -> C5H5 + H2O { A = 3.08E+06 n = 2.00 E = .00 }
1956     CP06f: C5H6 + O2 -> C5H5 + HO2 { A = 1.00E+14 n = .00 E = 155.44 }
1957     CP07f: C5H6 + HO2 -> C5H5 + H2O2 { A = 1.10E+04 n = 2.60 E = 53.97 }
1958     CP08f: C5H6 + CH3 -> C5H5 + CH4 { A = 1.80E-01 n = 4.00 E = .00 }
1959    
1960     # From CH4 + ?? (x0.5)
1961     CP09f: C5H6 + C2H3 -> C5H5 + C2H4 { A = 5.55E+04 n = 2.02 E = 13.17 }
1962     CP10f: C5H6 + A-C3H5 -> C5H5 + C3H6 { A = 2.15E+01 n = 3.31 E = 106.79 }
1963     CP11f: C5H6 + N-C4H5 -> C5H5 + C4H6 { A = 7.30E+10 n = 0.76 E = 63.51 }
1964    
1965    
1966     # Cyclopentadienyl radical
1967     # ------------------------
1968    
1969     # Moskaleva & Lin 2000
1970     # Knyazev & Slagle 2002
1971     CP16f: C3H3 + C2H2 -> C5H5 { A = 6.87E+55 n =-12.50 E = 175.80 }
1972    
1973     # Melius, Colvin, Marinov, Pitz, & Senkan 1996
1974     # Sharma & Green 2009 - Rate fitted at P=1bar
1975     # PRODUCTS TO BE CHECKED - Should be benzene?
1976     CP17 : C5H5 + CH3 -> C5H4CH2 + 2H { A = 4.91E+31 n = -4.85 E = 103.65 }
1977    
1978     # Murakami et al. 2003 - Total rate
1979     # Kislov & Mebel - Branching ratio
1980     CP18 : C5H5 + C5H5 -> A2-C10H8 + 2H { A = 6.39E+29 n = -4.03 E = 147.30 }
1981    
1982     # Robinson & Lindstedt 2011
1983     # estimated
1984     CP19f: C5H5 + C5H5 -> C9H7 + CH3 { A = 2.50E+12 n = .00 E = 40.00 }
1985    
1986     # Kislov & Mebel 2008 - Full entrance rate
1987     CP20 : C5H5 + C5H6 -> C9H8 + CH3 { A = 7.86E-01 n = 3.07 E = 23.97 }
1988    
1989     # Robinson & Lindstedt 2011
1990     CP21f: C5H5 + O -> N-C4H5 + CO { A = 1.27E+14 n = 0.26 E = 16.50 }
1991     CP22f: C5H5 + OH -> C4H6 + CO { A = 8.53E+13 n = 0.25 E = 18.20 }
1992     CP23f: C5H5 + OH -> C5H5O + H { A = 1.11E+05 n = 1.90 E = 138.60 }
1993     CP24f: C5H5 + O2 -> C5H4O + OH { A = 9.11E+15 n = -2.21 E = 10.20 }
1994     CP25f: C5H5 + O2 -> C5H5O + O { A = 4.37E+03 n = 2.40 E = 211.50 }
1995     CP26f: C5H5 + HO2 -> C5H5O + OH { A = 6.86E+13 n = 0.25 E = 21.30 }
1996    
1997    
1998     # Cyclopentadienoxy radical
1999     # -------------------------
2000    
2001     # Robinson & Lindstedt 2011
2002     CP27 : C5H5O -> C5H4O + H { A = 8.18E+16 n = -2.32 E = 36.50 }
2003     CP28 : C5H5O -> N-C4H5 + CO { A = 2.15E+64 n =-15.14 E = 278.00 }
2004    
2005     # 1/3 rate from CH3O
2006     CP29f: C5H5O + H -> C5H4O + H2 { A = 6.67E+12 n = .00 E = .00 }
2007     CP30f: C5H5O + O -> C5H4O + OH { A = 3.33E+12 n = .00 E = .00 }
2008     CP31f: C5H5O + OH -> C5H4O + H2O { A = 1.67E+12 n = .00 E = .00 }
2009     CP32f: C5H5O + O2 -> C5H4O + HO2 { A = 7.22E+09 n = .00 E = 7.32 }
2010    
2011    
2012     # Cyclopentadienone
2013     # -----------------
2014    
2015     # Wang & Brezinsky 1998
2016     # Ristori et al. 2001
2017     # (products guessed)
2018     CP33 : C5H4O -> 2 C2H2 + CO { A = 6.20E+41 n = -7.87 E = 413.00 }
2019     CP34 : C5H4O -> C4H4 + CO { A = 5.00E+11 n = .00 E = 221.80 }
2020    
2021     # From C2H4+R, C3H6+H
2022     # (products guessed)
2023     CP35 : C5H4O + H -> C2H3 + C2H2 + CO { A = 2.67E+12 n = 0.47 E = 22.72 }
2024     CP36 : C5H4O + O -> C3H3 + HCO + CO { A = 1.02E+08 n = 1.66 E = 2.75 }
2025    
2026    
2027    
2028     #==========================================================================#
2029     # #
2030     # "Detailed kinetic modeling of benzene and toluene oxidation #
2031     # at high temperatures" #
2032     # Zoran M. Djurisic - Master's Thesis #
2033     # http://diesel.me.berkeley.edu/~zoran/publications/2000_MS_Thesis/ #
2034     # #
2035     #==========================================================================#
2036    
2037    
2038     # Benzene
2039     # -------
2040    
2041     # Miller & Klippenstein 2003 (1bar)
2042     # Updated to include HPL from Harding et al. 2005
2043     BN00f: A1-C6H6 -> A1--C6H5 + H { A = 1.29E+61 n =-12.48 E = 619.59 }
2044    
2045     # Mebel & Lin 1997
2046     BN01f: A1-C6H6 + H -> A1--C6H5 + H2 { A = 6.02E+08 n = 1.80 E = 68.42 }
2047    
2048     # Lindsted & Skevis 1994
2049     BN02f: A1-C6H6 + O -> A1--C6H5 + OH { A = 2.00E+13 n = .00 E = 61.50 }
2050    
2051     # Seta, Nakajima & Miyoshi 2006
2052     BN03f: A1-C6H6 + OH -> A1--C6H5 + H2O { A = 2.34E+04 n = 2.68 E = 3.07 }
2053     BN04f: A1-C6H6 + OH -> A1OH-C6H6O + H { A = 1.32E+02 n = 3.25 E = 23.39 }
2054    
2055     # From C2H4 + O2 (x1.5)
2056     # Hua, Ruscic, Wang 2005
2057     # Backward ~ 2e12
2058     BN05f: A1-C6H6 + O2 -> A1--C6H5 + HO2 { A = 4.34E+14 n = .00 E = 269.00 }
2059    
2060     # Taatjes, Wang, et al. 2010
2061     # Refitted
2062     BN06f: A1-C6H6 + O -> A1O-C6H5O + H { A = 1.99E+07 n = 1.80 E = 16.63 }
2063     BN07f: A1-C6H6 + O -> A1OH-C6H6O { A = 1.53E+10 n = 0.92 E = 13.79 }
2064     BN08f: A1-C6H6 + O -> C5H6 + CO { A = 1.53E+17 n = -0.89 E = 64.89 }
2065    
2066    
2067     # Phenyl radical
2068     # --------------
2069    
2070     # Wang et al. 2000
2071     BN09f: A1--C6H5 + M9 -> O-C6H4 + H + M9 { A = 1.00E+84 n =-18.87 E = 376.98
2072     Ai= 4.30E+12 ni= 0.62 Ei= 323.43
2073     fcA = 0.098 fctA = 696
2074     fcb = 0.902 fctb = 358
2075     fcc = 1.0 fctc = 3856 }
2076    
2077     # da Silva, Chen & Bozzelli 2007
2078     # From 3/4-methylphenyl + O2
2079     BN10f: A1--C6H5 + O2 -> A1O-C6H5O + O { A = 8.57E+20 n = -2.27 E = 30.08 }
2080    
2081     # Frank, Herzler, Just & Wahl 1994
2082     BN11f: A1--C6H5 + O2 -> OC6H4O + H { A = 3.00E+13 n = .00 E = 37.58 }
2083     BN12f: A1--C6H5 + O -> A1O-C6H5O { A = 1.00E+14 n = .00 E = .00 }
2084    
2085     BN13f: A1--C6H5 + OH -> A1O-C6H5O + H { A = 3.00E+13 n = .00 E = .00 }
2086     BN14f: A1--C6H5 + HO2 -> A1O-C6H5O + OH { A = 3.00E+13 n = .00 E = .00 }
2087    
2088     # Tokmakov & Lin 1999/2002
2089     BN15f: A1--C6H5 + CH4 -> A1-C6H6 + CH3 { A = 3.89E-03 n = 4.57 E = 22.00 }
2090    
2091    
2092     # Phenol
2093     # ------
2094    
2095     # Xu & Lin 2006
2096     # Rates for 1 atm
2097     # Formation of CO x0.765 to better match Horn & Roy 1989
2098     BN16f: A1OH-C6H6O -> C5H6 + CO { A = 6.59E+15 n = -0.61 E = 310.11 }
2099     BN17f: A1OH-C6H6O -> A1O-C6H5O + H { A = 1.01E+71 n =-15.92 E = 522.12 }
2100    
2101     # From CH3OH+R
2102     BN18f: A1OH-C6H6O + H -> A1O-C6H5O + H2 { A = 4.20E+06 n = 2.10 E = 20.38 }
2103     BN19f: A1OH-C6H6O + OH -> A1O-C6H5O + H2O { A = 6.30E+06 n = 2.00 E = 6.28 }
2104     BN20f: A1OH-C6H6O + CH3 -> A1O-C6H5O + CH4 { A = 1.00E+07 n = 1.50 E = 41.59 }
2105    
2106     # Brezinsky et al. 1998
2107     #N21f: A1OH-C6H6O + O2 -> A1O-C6H5O + HO2 { A = 7.32E+13 n = .00 E = 173.22 }
2108    
2109    
2110     # Phenoxy radical
2111     # 2-B1 state for O=C6H5
2112     # ---------------------
2113    
2114     # Murakami et al. 2003
2115     BN22f: A1O-C6H5O -> C5H5 + CO { A = 2.90E+10 n = .00 E = 152.40 }
2116    
2117     # From C2H5 + O (x2)
2118     BN23f: A1O-C6H5O + O -> OC6H4O + H { A = 6.34E+13 n = 0.03 E = -1.65 }
2119    
2120     # From A-C3H5 + O2 - Total rate (x3/2)
2121     BN24f: A1O-C6H5O + O2 -> OC6H4O + OH { A = 6.51E+07 n = 1.30 E = 73.92 }
2122    
2123    
2124     # p-Benzoquinone
2125     # Thermoprop & Reactions for para
2126     # -------------------------------
2127    
2128     BN25 : OC6H4O -> C5H4O + CO { A = 7.40E+11 n = .00 E = 246.86 }
2129    
2130     BN26 : OC6H4O + H -> C5H5O + CO { A = 4.30E+09 n = 1.45 E = 16.18 }
2131     BN27 : OC6H4O + O -> CH2CO + C2H2 + 2 CO { A = 3.00E+13 n = .00 E = 20.92 }
2132    
2133    
2134     # Benzyne
2135     # -------
2136    
2137     # Wang, Laskin, Moriarty, Frenklach 2000
2138     BN28 : O-C6H4 -> C4H2 + C2H2 { A = 1.20E+18 n = -0.34 E = 367.48 }
2139    
2140     # Wang & Frenklach 1997
2141     BN29f: N-C4H3 + C2H2 -> O-C6H4 + H { A = 6.90E+46 n =-10.01 E = 125.94 }
2142    
2143     BN30 : O-C6H4 + OH -> C5H5 + CO { A = 1.00E+13 n = .00 E = .00 }
2144    
2145    
2146    
2147     #==========================================================================#
2148     # #
2149     # Toluene chemistry #
2150     # #
2151     # Oehlschlaeger, Davidson & Hanson, Comb. Flame, 2006, 147, 195-208 #
2152     # #
2153     #==========================================================================#
2154    
2155    
2156     # Toluene / Benzyl decomposition
2157     # ------------------------------
2158    
2159     # Tokmakov et al. 2001 (x1.2 to match exp.)
2160     # Sheen, Rosado-Reyes, Tsang 2013 (within 2%)
2161     T01f: A1CH3-C7H8 + H -> A1-C6H6 + CH3 { A = 2.31E+06 n = 2.17 E = 17.42 }
2162    
2163     # Klippenstein et al. 2007
2164     # Almost indep or pressure => HPL
2165     T02f: A1CH3-C7H8 -> A1CH2-C7H7 + H { A = 1.56E+13 n = 0.68 E = 373.24 }
2166     T03f: A1CH3-C7H8 -> A1--C6H5 + CH3 { A = 4.35E+22 n = -1.73 E = 436.01 }
2167     # P=1bar - 1000K-2500K
2168     T04f: A1CH2-C7H7 + H -> A1--C6H5 + CH3 { A = 5.83E+67 n =-14.15 E = 285.89 }
2169    
2170     # Assumed products. Other choices: C7H6 + H, c-C7H7
2171     # Rate from Oehlschlaeger et al. 2006 (1.5 atm)
2172     T05f: A1CH2-C7H7 -> C5H5 + C2H2 { A = 8.20E+14 n = .00 E = 337.55 }
2173    
2174    
2175     # Toluene
2176     # -------
2177    
2178     # Oehlschlaeger et al. 2006 (1.5 atm)
2179     T06f: A1CH3-C7H8 + H -> A1CH2-C7H7 + H2 { A = 6.47E+00 n = 3.98 E = 14.16 }
2180    
2181     # From C3H8+O (x0.5)
2182     T07f: A1CH3-C7H8 + O -> A1CH2-C7H7 + OH { A = 9.50E+04 n = 2.68 E = 15.55 }
2183    
2184     # From A1+O (x5/6)
2185     T08f: A1CH3-C7H8 + O -> OA1CH3-C7H7O + H { A = 1.66E+07 n = 1.80 E = 16.63 }
2186     T09f: A1CH3-C7H8 + O -> HOA1CH3-C7H8O { A = 1.28E+10 n = 0.92 E = 13.79 }
2187    
2188     # Seta, Nakajima & Miyoshi 2006
2189     # Better match with Vasudevan, Davidson & Hanson 2005
2190     T10f: A1CH3-C7H8 + OH -> A1CH2-C7H7 + H2O { A = 1.77E+05 n = 2.39 E = -2.52 }
2191     T11f: A1CH3-C7H8 + OH -> A1OH-C6H6O + CH3 { A = 7.83E+02 n = 2.88 E = 13.48 }
2192     T12f: A1CH3-C7H8 + OH -> HOA1CH3-C7H8O + H { A = 3.14E+01 n = 3.37 E = 19.75 }
2193    
2194     # Oehlschlaeger et al. 2006 (1.5 atm)
2195     T13f: A1CH3-C7H8 + O2 -> A1CH2-C7H7 + HO2 { A = 2.18E+07 n = 2.50 E = 192.65 }
2196    
2197     # Baulch et al. 2005
2198     T14f: A1CH3-C7H8 + HO2 -> A1CH2-C7H7 + H2O2 { A = 9.33E+04 n = 2.50 E = 61.44 }
2199    
2200     # From C3H8+CH3 (x0.5)
2201     T15f: A1CH3-C7H8 + CH3 -> A1CH2-C7H7 + CH4 { A = 4.52E-01 n = 3.65 E = 29.93 }
2202    
2203     # Heckmann, Hippler & Troe 1996
2204     T16f: A1CH3-C7H8 + A1--C6H5 -> A1CH2-C7H7 + A1-C6H6 { A = 7.94E+13 n = .00 E = 50.00 }
2205    
2206    
2207     # Benzyl radical
2208     # --------------
2209    
2210     # da Silva & Bozzelli 2012 - P=1atm
2211     T17f: A1CH2-C7H7 + O -> A1-C6H6 + HCO { A = 6.98E+12 n = 0.33 E = 2.87 }
2212     T18f: A1CH2-C7H7 + O -> A1CHO-C7H6O + H { A = 2.75E+13 n = 0.07 E = 3.06 }
2213    
2214     # Murakami et al. 2007 - HPL
2215     # Canneaux et al. 2008 - Benzylperoxy isomerization
2216     # Benzylperoxy in Steady State
2217     T19f: A1CH2-C7H7 + O2 -> A1CHO-C7H6O + OH { A = 3.76E+15 n = -1.55 E = 47.37 }
2218    
2219     # da Silva & Bozzelli 2008
2220     T21f: A1CH2-C7H7 + HO2 -> A1CH2O-C7H7O + OH { A = 1.19E+09 n = 1.03 E = -9.41 }
2221    
2222     # From A-C3H5
2223     T22 : A1CH2-C7H7 + C3H3 -> A2-C10H8 + 2H { A = 1.88E+38 n = -7.53 E = 99.91 }
2224    
2225    
2226     # Alcoxy Benzyl
2227     # -------------
2228    
2229     # Choi, Xia, Park & Lin 2000
2230     T23f: A1--C6H5 + CH2O -> A1-C6H6 + HCO { A = 8.55E+04 n = 2.19 E = 0.16 }
2231    
2232     # Xia & Lin 2000
2233     T24f: A1CH2O-C7H7O -> A1CHO-C7H6O + H { A = 1.27E+13 n = .00 E = 86.19 }
2234    
2235     # da Silva & Bozzelli 2009 - P=1atm
2236     T25f: A1CH2O-C7H7O -> A1--C6H5 + CH2O { A = 7.21E+33 n = -6.21 E = 154.18 }
2237     T26f: A1CH2O-C7H7O -> A1-C6H6 + HCO { A = 2.37E+32 n = -6.10 E = 120.54 }
2238    
2239     # From CH3O (x2/3)
2240     T27f: A1CH2O-C7H7O + H -> A1CHO-C7H6O + H2 { A = 1.33E+13 n = .00 E = .00 }
2241     T28f: A1CH2O-C7H7O + O -> A1CHO-C7H6O + OH { A = 6.67E+12 n = .00 E = .00 }
2242     T29f: A1CH2O-C7H7O + OH -> A1CHO-C7H6O + H2O { A = 3.33E+12 n = .00 E = .00 }
2243     T30f: A1CH2O-C7H7O + O2 -> A1CHO-C7H6O + HO2 { A = 4.11E+10 n = .00 E = 7.32 }
2244    
2245    
2246     # Benzaldehyde
2247     # ------------
2248    
2249     # From CH3CHO - Baulch et al. 2005
2250     # Grela & Colussi 1986 - Loss of H then loss of CO
2251     T31 : A1CHO-C7H6O -> A1--C6H5 + CO + H { A = 2.10E+16 n = .00 E = 342.00 }
2252    
2253     # From CH3CHO
2254     T32 : A1CHO-C7H6O + H -> A1--C6H5 + CO + H2 { A = 2.05E+09 n = 1.16 E = 10.06 }
2255     T33 : A1CHO-C7H6O + O -> A1--C6H5 + CO + OH { A = 2.92E+12 n = .00 E = 7.57 }
2256     T34 : A1CHO-C7H6O + OH -> A1--C6H5 + CO + H2O { A = 2.34E+10 n = .73 E = -4.66 }
2257     T35 : A1CHO-C7H6O + CH3 -> A1--C6H5 + CO + CH4 { A = 2.72E+06 n = 1.77 E = 24.77 }
2258    
2259    
2260     # Cresol
2261     # All isomers lumped into meta
2262     # ----------------------------
2263    
2264     # From A1OH/A1O
2265     T36f: HOA1CH3-C7H8O -> OA1CH3-C7H7O + H { A = 1.01E+71 n =-15.92 E = 522.12 }
2266     T37f: HOA1CH3-C7H8O + H -> OA1CH3-C7H7O + H2 { A = 4.20E+06 n = 2.10 E = 20.38 }
2267     T38f: HOA1CH3-C7H8O + O -> OA1CH3-C7H7O + OH { A = 1.30E+05 n = 2.50 E = 20.92 }
2268     T39f: HOA1CH3-C7H8O + OH -> OA1CH3-C7H7O + H2O { A = 6.30E+06 n = 2.00 E = 6.28 }
2269     T40f: HOA1CH3-C7H8O + CH3-> OA1CH3-C7H7O + CH4 { A = 1.00E+07 n = 1.50 E = 41.59 }
2270    
2271     T41 : OA1CH3-C7H7O -> C5H4CH2 + CO + H { A = 2.90E+10 n = .00 E = 152.40 }
2272    
2273    
2274     # Methyl-phenyl
2275     # All isomers lumped into meta
2276     # ----------------------------
2277    
2278     # From A1 (x0.65)
2279     # From symmetry should be x5/6
2280     # Seta, Nakajima & Miyoshi 2006 - Rate for OH - Same as A1 x0.65
2281     T42f: A1CH3-C7H8 -> A1CH3*-C7H7 + H { A = 8.39E+60 n =-12.48 E = 619.59 }
2282     T43f: A1CH3-C7H8 + H -> A1CH3*-C7H7 + H2 { A = 3.91E+08 n = 1.80 E = 68.42 }
2283     T44f: A1CH3-C7H8 + O -> A1CH3*-C7H7 + OH { A = 1.60E+13 n = .00 E = 61.50 }
2284     T45f: A1CH3-C7H8 + OH -> A1CH3*-C7H7 + H2O { A = 1.36E+04 n = 2.69 E = 2.59 }
2285     T46f: A1CH3-C7H8 + CH3 -> A1CH3*-C7H7 + CH4 { A = 1.79E-02 n = 4.46 E = 57.06 }
2286    
2287     # From A1-
2288     T47f: A1CH3*-C7H7 + O -> OA1CH3-C7H7O { A = 1.00E+14 n = .00 E = .00 }
2289     T48f: A1CH3*-C7H7 + OH -> OA1CH3-C7H7O + H { A = 3.00E+13 n = .00 E = .00 }
2290     T49f: A1CH3*-C7H7 + HO2 -> OA1CH3-C7H7O + OH { A = 3.00E+13 n = .00 E = .00 }
2291    
2292     # da Silva, Chen & Bozzelli 2007
2293     # Assumed products for methyloxepinoxy decomposition
2294     T50f: A1CH3*-C7H7 + O2 -> OA1CH3-C7H7O + O { A = 8.57E+20 n = -2.27 E = 30.08 }
2295     T51 : A1CH3*-C7H7 + O2 -> C5H4CH2 + CO2 + H { A = 2.55E+13 n = -0.44 E = -6.90 }
2296     T52 : A1CH3*-C7H7 + O2 -> P-C3H4 + C2H3 + 2CO { A = 2.55E+13 n = -0.44 E = -6.90 }
2297    
2298    
2299    
2300     #===============================================================================#
2301     # #
2302     # Styrene Chemistry #
2303     # Adapted from C2H4 chemistry #
2304     # Additional rates from Kislov & Mebel 2005 #
2305     # #
2306     #===============================================================================#
2307    
2308    
2309     # Styrene
2310     # -------
2311    
2312     # Greda et al. 1992
2313     ST01 : A1C2H3-C8H8 -> A1-C6H6 + H2C2 { A = 2.40E+14 n = .00 E = 326.90 }
2314    
2315     # Wang & Frenklach 1997 - estimated HPL
2316     ST02f: A1--C6H5 + C2H3 -> A1C2H3-C8H8 { A = 6.00E+12 n = .00 E = .00 }
2317    
2318     # Tokmakov & Lin 2004
2319     ST03f: A1--C6H5 + C2H4 -> A1C2H3-C8H8 + H { A = 3.62E+28 n = -4.24 E = 99.85 }
2320     ST04f: A1C2H3-C8H8 + H -> A1-C6H6 + C2H3 { A = 5.62E+24 n = -3.00 E = 82.97 }
2321    
2322     # From A1CH3
2323     ST05f: A1C2H3-C8H8 + OH -> A1OH-C6H6O + C2H3 { A = 7.83E+02 n = 2.88 E = 13.48 }
2324    
2325     # From C2H4 (x0.5)
2326     ST06f: A1C2H3-C8H8 -> A1C2H2-C8H7 + H { A = 3.01E+14 n = 0.34 E = 465.49 }
2327     ST07f: A1C2H3-C8H8 + H -> A1C2H2-C8H7 + H2 { A = 6.35E+04 n = 2.75 E = 48.74 }
2328     ST08f: A1C2H3-C8H8 + OH -> A1C2H2-C8H7 + H2O { A = 1.12E+04 n = 2.75 E = 9.27 }
2329    
2330     # From A1 (x1/3)
2331     ST09f: A1C2H3-C8H8 -> A1C2H3*-C8H7 + H { A = 4.30E+60 n =-12.48 E = 619.59 }
2332     ST10f: A1C2H3-C8H8 + H -> A1C2H3*-C8H7 + H2 { A = 2.01E+08 n = 1.80 E = 68.42 }
2333     ST11f: A1C2H3-C8H8 + OH -> A1C2H3*-C8H7 + H2O { A = 7.80E+03 n = 2.68 E = 3.07 }
2334    
2335     # From C2H4 (x0.5)
2336     # Half for each carbon atoms
2337     ST12f: A1C2H3-C8H8 + O -> A1CH2-C7H7 + HCO { A = 1.95E+08 n = 1.36 E = 3.71 }
2338     ST13f: A1C2H3-C8H8 + O -> A1CHO-C7H6O + T-CH2 { A = 3.58E+04 n = 2.47 E = 3.89 }
2339    
2340    
2341     # Styryl radical
2342     # --------------
2343    
2344     # Tolkmakov & Lin 2003
2345     ST16f: A1--C6H5 + C2H2 -> A1C2H-C8H6 + H { A = 2.66E+32 n = -5.30 E = 99.52 }
2346     ST17f: A1--C6H5 + C2H2 -> A1C2H2-C8H7 { A = 4.80E+44 n = -9.90 E = 73.75 }
2347    
2348     # Kislov & Mebel 2005 - HPL
2349     ST18f: A1C2H2-C8H7 -> A1C2H3*-C8H7 { A = 5.90E+10 n = 0.55 E = 115.34 }
2350    
2351     # From N-C4H5
2352     ST19f: A1C2H2-C8H7 -> A1C2H-C8H6 + H { A = 1.81E+54 n =-12.69 E = 215.02 }
2353     ST20f: A1C2H2-C8H7 + H -> A1C2H-C8H6 + H2 { A = 1.50E+13 n = .00 E = .00 }
2354     ST21f: A1C2H2-C8H7 + OH -> A1C2H-C8H6 + H2O { A = 2.50E+12 n = .00 E = .00 }
2355     ST22f: A1C2H2-C8H7 + O2 -> A1C2H-C8H6 + HO2 { A = 6.70E+05 n = 1.61 E = -1.61 }
2356    
2357     # From C2H3 + O
2358     ST23f: A1C2H2-C8H7 + O -> A1CH2-C7H7 + CO { A = 1.03E+13 n = 0.21 E = -1.79 }
2359    
2360     # From C2H3 + O2
2361     ST24 : A1C2H2-C8H7 + O2 -> A1CH2-C7H7 + CO + O { A = 3.03E+11 n = 0.29 E = 0.05 }
2362     ST25f: A1C2H2-C8H7 + O2 -> A1CHO-C7H6O + HCO { A = 4.58E+16 n = -1.39 E = 4.25 }
2363    
2364    
2365     # Ethynylbenzene
2366     # --------------
2367    
2368     # Goulay & Leone 2006
2369     # Woon, Park & Jin-Young 2009
2370     ST26f: A1-C6H6 + C2H -> A1C2H-C8H6 + H { A = 2.00E+14 n = .00 E = .00 }
2371    
2372     # From A1 (x1/3)
2373     ST27f: A1C2H-C8H6 -> A1C2H*-C8H5 + H { A = 4.30E+60 n =-12.48 E = 619.59 }
2374     ST28f: A1C2H-C8H6 + H -> A1C2H*-C8H5 + H2 { A = 2.01E+08 n = 1.80 E = 68.42 }
2375     ST29f: A1C2H-C8H6 + OH -> A1C2H*-C8H5 + H2O { A = 7.80E+03 n = 2.68 E = 3.07 }
2376    
2377     # From C2H2
2378     ST30f: A1C2H-C8H6 + O -> A1--C6H5 + HCCO { A = 3.70E+09 n = 1.28 E = 10.34 }
2379    
2380     ST31f: A1C2H-C8H6 + OH -> A1--C6H5 + CH2CO { A = 2.10E+01 n = 3.22 E = -1.76 }
2381     ST32f: A1C2H-C8H6 + OH -> A1CH2-C7H7 + CO { A = 6.40E+08 n = 0.73 E = 10.79 }
2382    
2383    
2384    
2385     #==========================================================================#
2386     # #
2387     # Ethyl-Benzene chemistry #
2388     # #
2389     # Adapted from C3H8 and Toluene/Benzene chemistry #
2390     # #
2391     #==========================================================================#
2392    
2393    
2394     # Ethylbenzene
2395     # ------------
2396    
2397     # Estimated from C3H7+H - HPL
2398     EB01f: A1C2H4-C8H9 + H -> A1C2H5-C8H10 { A = 3.61E+13 n = .00 E = .00 }
2399    
2400     # Estimated from C2H5+CH3 - HPL
2401     EB02f: A1CH2-C7H7 + CH3 -> A1C2H5-C8H10 { A = 2.00E+13 n = .00 E = .00 }
2402     EB03f: A1--C6H5 + C2H5 -> A1C2H5-C8H10 { A = 2.00E+13 n = .00 E = .00 }
2403    
2404     # From A1CH3
2405     EB04f: A1C2H5-C8H10 + H -> A1-C6H6 + C2H5 { A = 2.31E+06 n = 2.17 E = 17.42 }
2406     EB05f: A1C2H5-C8H10 + OH -> A1OH-C6H6O + C2H5 { A = 7.83E+02 n = 2.88 E = 13.48 }
2407    
2408     # From C3H8 (x0.5)
2409     EB06f: A1C2H5-C8H10 + H -> A1C2H4-C8H9 + H2 { A = 4.68E+07 n = 1.97 E = 34.31 }
2410     EB07f: A1C2H5-C8H10 + O -> A1C2H4-C8H9 + OH { A = 9.95E+04 n = 2.68 E = 15.55 }
2411     EB08f: A1C2H5-C8H10 + OH -> A1C2H4-C8H9 + H2O { A = 2.67E+03 n = 2.94 E = -1.75 }
2412     EB09f: A1C2H5-C8H10 + CH3 -> A1C2H4-C8H9 + CH4 { A = 4.52E-01 n = 3.65 E = 29.93 }
2413     EB10f: A1C2H5-C8H10 + HO2 -> A1C2H4-C8H9 + H2O2 { A = 2.38E+04 n = 2.55 E = 69.00 }
2414    
2415    
2416     # N-Ethylbenzene radical
2417     # ----------------------
2418    
2419     # Tokmakov & Lin 2004
2420     # HPL for both decompositions
2421     EB11f: A1C2H4-C8H9 -> A1--C6H5 + C2H4 { A = 1.72E+11 n = 0.78 E = 161.94 }
2422     EB12f: A1C2H4-C8H9 -> A1C2H3-C8H8 + H { A = 3.79E+06 n = 1.99 E = 134.33 }
2423    
2424     # From C3H7
2425     EB13f: A1C2H4-C8H9 + H -> A1C2H3-C8H8 + H2 { A = 1.80E+12 n = .00 E = .00 }
2426     EB14f: A1C2H4-C8H9 + OH -> A1C2H3-C8H8 + H2O { A = 2.41E+13 n = .00 E = .00 }
2427     EB15f: A1C2H4-C8H9 + O2 -> A1C2H3-C8H8 + HO2 { A = 3.70E+16 n = -1.63 E = 14.30 }
2428     EB16f: A1C2H4-C8H9 + CH3 -> A1C2H3-C8H8 + CH4 { A = 3.31E+12 n = .00 E = -3.22 }
2429    
2430     EB17f: A1C2H4-C8H9 + O -> A1CH2-C7H7 + CH2O { A = 9.60E+13 n = .00 E = .00 }
2431    
2432     # From NC7
2433     EB18 : A1C2H4-C8H9 + HO2 -> A1CH2-C7H7 + CH2O + OH { A = 7.00E+12 n = .00 E = -4.18 }
2434     EB19 : A1C2H4-C8H9 + CH3O2 -> A1CH2-C7H7 + CH2O + CH3O { A = 7.00E+12 n = .00 E = -4.18 }
2435    
2436    
2437    
2438     #=========================================================================#
2439     # #
2440     # Xylene Oxidation Chemistry #
2441     # Adapted from Toluene Chemistry #
2442     # #
2443     #=========================================================================#
2444    
2445    
2446     # Xylene
2447     # ------
2448    
2449     # From A1CH3 (x2)
2450     XY01f: A1CH3CH3-C8H10 -> A1CH3CH2-C8H9 + H { A = 2.12E+13 n = 0.68 E = 373.24 }
2451     XY02f: A1CH3CH3-C8H10 -> A1CH3*-C7H7 + CH3 { A = 8.70E+22 n = -1.73 E = 436.01 }
2452    
2453     # From A1CH3+R (x2)
2454     XY03f: A1CH3CH3-C8H10 + H -> A1CH3CH2-C8H9 + H2 { A = 1.29E+01 n = 3.98 E = 14.16 }
2455     XY04f: A1CH3CH3-C8H10 + O -> A1CH3CH2-C8H9 + OH { A = 1.90E+05 n = 2.68 E = 15.55 }
2456     XY05f: A1CH3CH3-C8H10 + OH -> A1CH3CH2-C8H9 + H2O { A = 3.54E+05 n = 2.39 E = -2.52 }
2457     XY06f: A1CH3CH3-C8H10 + O2 -> A1CH3CH2-C8H9 + HO2 { A = 4.36E+07 n = 2.50 E = 192.65 }
2458     XY07f: A1CH3CH3-C8H10 + HO2 -> A1CH3CH2-C8H9 + H2O2 { A = 1.87E+05 n = 2.50 E = 61.44 }
2459     XY08f: A1CH3CH3-C8H10 + CH3 -> A1CH3CH2-C8H9 + CH4 { A = 9.03E-01 n = 3.65 E = 29.93 }
2460    
2461     # From A1CH3+X (x2)
2462     XY09f: A1CH3CH3-C8H10 + H -> A1CH3-C7H8 + CH3 { A = 4.62E+06 n = 2.17 E = 17.42 }
2463     XY10f: A1CH3CH3-C8H10 + OH -> HOA1CH3-C7H8O + CH3 { A = 1.57E+03 n = 2.88 E = 13.48 }
2464    
2465     # !!!! CAREFUL !!!!
2466     # Path from Bounaceur et al. 2005
2467     # Rate from A1+O (x2/3)
2468     XY11 : A1CH3CH3-C8H10 + O -> A1CH3-C7H8 + CO + 2H { A = 1.82E+08 n = 1.55 E = 12.93 }
2469    
2470    
2471     # Xylyl radical
2472     # -------------
2473    
2474     # Path from Bournaceur et al. 2005
2475     # Rate from A1CH2
2476     XY12 : A1CH3CH2-C8H9 -> A1-C6H6 + H + C2H2 { A = 8.20E+14 n = .00 E = 337.55 }
2477    
2478     XY13f: A1CH3CH2-C8H9 + H -> A1CH3*-C7H7 + CH3 { A = 5.83E+67 n =-14.15 E = 285.89 }
2479    
2480     # From A1CH2+O
2481     XY14f: A1CH3CH2-C8H9 + O -> A1CH3CHO-C8H8O + H { A = 2.75E+13 n = 0.07 E = 3.06 }
2482     XY15f: A1CH3CH2-C8H9 + O -> A1CH3-C7H8 + HCO { A = 6.98E+12 n = 0.33 E = 2.87 }
2483    
2484     # From A1CH2+O2
2485     # Addition from Murakami et al. 2009
2486     # Peroxy isomerization from Canneaux et al. 2008
2487     XY16f: A1CH3CH2-C8H9 + O2 -> A1CH3CHO-C8H8O + OH { A = 1.38E+02 n = 2.42 E = 31.13 }
2488    
2489     # From A1CH2+HO2
2490     # Assumed unique decomposition into A1CHO+H
2491     XY19 : A1CH3CH2-C8H9 + HO2 -> A1CH3CHO-C8H8O + H + OH { A = 1.19E+09 n = 1.03 E = -9.41 }
2492    
2493     # From A-C3H5 + C3H3
2494     XY20 : A1CH3CH2-C8H9 + C3H3 -> A2CH3-C11H10 + 2H { A = 1.88E+38 n = -7.53 E = 99.91 }
2495    
2496    
2497     # Tolualdehyde
2498     # ------------
2499    
2500     # From A1CH3 & A1CHO decomposition
2501     XY21f: A1CH3CHO-C8H8O -> A1CHOCH2-C8H7O + H { A = 1.56E+13 n = 0.68 E = 373.24 }
2502     XY22 : A1CH3CHO-C8H8O -> A1--C6H5 + CO + CH3 { A = 4.35E+22 n = -1.73 E = 436.01 }
2503     XY23 : A1CH3CHO-C8H8O -> A1CH3*-C7H7 + CO + H { A = 2.10E+16 n = .00 E = 342.00 }
2504    
2505     # From A1CH3+R
2506     XY24f: A1CH3CHO-C8H8O + H -> A1CHOCH2-C8H7O + H2 { A = 6.47E+00 n = 3.98 E = 14.16 }
2507     XY25f: A1CH3CHO-C8H8O + O -> A1CHOCH2-C8H7O + OH { A = 9.50E+04 n = 2.68 E = 15.55 }
2508     XY26f: A1CH3CHO-C8H8O + OH -> A1CHOCH2-C8H7O + H2O { A = 1.77E+05 n = 2.39 E = -2.52 }
2509     XY27f: A1CH3CHO-C8H8O + CH3 -> A1CHOCH2-C8H7O + CH4 { A = 4.52E-01 n = 3.65 E = 29.93 }
2510    
2511     # From A1CHO+R
2512     XY28 : A1CH3CHO-C8H8O + H -> A1CH3*-C7H7 + CO + H2 { A = 2.05E+09 n = 1.16 E = 10.06 }
2513     XY29 : A1CH3CHO-C8H8O + O -> A1CH3*-C7H7 + CO + OH { A = 2.92E+12 n = .00 E = 7.57 }
2514     XY30 : A1CH3CHO-C8H8O + OH -> A1CH3*-C7H7 + CO + H2O { A = 2.34E+10 n = 0.73 E = -4.66 }
2515     XY31 : A1CH3CHO-C8H8O + CH3 -> A1CH3*-C7H7 + CO + CH4 { A = 2.72E+06 n = 1.77 E = 24.77 }
2516    
2517    
2518     # Tolualdehyde radical
2519     # --------------------
2520    
2521     # From A1CH2+O
2522     XY32f: A1CHOCH2-C8H7O + O -> A1CHOCHO-C8H6O2 + H { A = 2.75E+13 n = 0.07 E = 3.06 }
2523     XY33f: A1CHOCH2-C8H7O + O -> A1CHO-C7H6O + HCO { A = 6.98E+12 n = 0.33 E = 2.87 }
2524    
2525     # From A1CH2+HO2
2526     # Assumed unique decomposition into A1CHO+H
2527     XY33 : A1CHOCH2-C8H7O + HO2 -> A1CHOCHO-C8H6O2 + H + OH { A = 1.19E+09 n = 1.03 E = -9.41 }
2528    
2529    
2530     # Phthalaldehyde
2531     # --------------
2532    
2533     # From A1CHO decomposition (x2)
2534     XY34 : A1CHOCHO-C8H6O2 -> A1--C6H5 + 2 CO + H { A = 4.20E+16 n = .00 E = 342.00 }
2535    
2536     # From A1CHO+R (x2)
2537     XY35 : A1CHOCHO-C8H6O2 + H -> A1CHO-C7H6O + CO + H { A = 4.10E+09 n = 1.16 E = 10.06 }
2538     XY36 : A1CHOCHO-C8H6O2 + O -> A1CHO-C7H6O + CO + O { A = 5.84E+12 n = .00 E = 7.57 }
2539     XY37 : A1CHOCHO-C8H6O2 + OH -> A1CHO-C7H6O + CO + OH { A = 4.68E+10 n = 0.73 E = -4.66 }
2540     XY38 : A1CHOCHO-C8H6O2 + CH3 -> A1CHO-C7H6O + CO + CH3 { A = 5.44E+06 n = 1.77 E = 24.77 }
2541    
2542    
2543    
2544     #==========================================================================#
2545     # #
2546     # Indene chemistry #
2547     # Adapted from Cyclopentadiene #
2548     # #
2549     #==========================================================================#
2550    
2551    
2552     # Indene
2553     # ------
2554    
2555     # Kislov & Mebel 2007
2556     # Rate estimated
2557     I00f: A1--C6H5 + C3H3 -> C9H8 { A = 1.00E+13 n = .00 E = .00 }
2558    
2559     # Kislov & Mebel 2007
2560     I01f: A1CH2-C7H7 + C2H2 -> C9H8 + H { A = 3.16E+04 n = 2.48 E = 46.28 }
2561    
2562     I02f: C9H8 -> C9H7 + H { A = 3.24E+49 n =-10.01 E = 423.40 }
2563     I03f: C9H8 + H -> C9H7 + H2 { A = 8.59E+07 n = 1.85 E = 13.97 }
2564    
2565     I05f: C9H8 + O -> C9H7 + OH { A = 4.77E+04 n = 2.71 E = 4.63 }
2566     I06f: C9H8 + OH -> C9H7 + H2O { A = 3.08E+06 n = 2.00 E = .00 }
2567     I07f: C9H8 + O2 -> C9H7 + HO2 { A = 1.00E+14 n = .00 E = 155.44 }
2568     I08f: C9H8 + HO2 -> C9H7 + H2O2 { A = 1.10E+04 n = 2.60 E = 53.97 }
2569     I09f: C9H8 + CH3 -> C9H7 + CH4 { A = 1.80E-01 n = 4.00 E = .00 }
2570    
2571     # From C2H4 + O
2572     #I10 : C9H8 + O -> O-C6H4 + C2H3 + CO + H { A = 1.02E+08 n = 1.66 E = 2.75 }
2573    
2574    
2575     # Indenyl radical
2576     # 2/5 of the rate for C5H5
2577     # ------------------------
2578    
2579     I12 : C9H7 + C5H5 -> A3-C14H10 + 2H { A = 2.56E+29 n = -4.03 E = 147.30 }
2580     I13 : C9H7 + CH3 -> A2-C10H8 + 2H { A = 1.96E+31 n = -4.85 E = 103.65 }
2581    
2582     # TEST - GB
2583     #I14 : C9H7 -> C5H5 + C4H2 { A = 1.00E+10 n= .00 E = 250.00 }
2584    
2585     I15 : C9H7 + O -> A1C2H2-C8H7 + CO { A = 5.08E+13 n = 0.26 E = 16.50 }
2586     I16 : C9H7 + OH -> A1C2H3-C8H8 + CO { A = 3.41E+13 n = 0.25 E = 18.20 }
2587     I17 : C9H7 + OH -> C9H6O + 2H { A = 4.44E+04 n = 1.90 E = 138.60 }
2588     I18 : C9H7 + O2 -> C9H6O + OH { A = 3.64E+15 n = -2.21 E = 10.20 }
2589     I19 : C9H7 + O2 -> C9H6O + O + H { A = 1.75E+03 n = 2.40 E = 211.50 }
2590     I20 : C9H7 + HO2 -> C9H6O + OH + H { A = 2.74E+13 n = 0.25 E = 21.30 }
2591    
2592     # From A-C3H5 + C3H3
2593     I21 : C9H7 + C3H3 -> A2R5-C12H8 + 2H { A = 1.88E+38 n = -7.53 E = 99.91 }
2594    
2595    
2596     # Indenone
2597     # --------
2598    
2599     I22 : C9H6O -> O-C6H4 + C2H2 + CO { A = 6.20E+41 n = -7.87 E = 413.00 }
2600    
2601     I23 : C9H6O + H -> A1C2H2-C8H7 + CO { A = 1.37E+09 n = 1.46 E = 5.67 }
2602     I24 : C9H6O + O -> O-C6H4 + CH2CO + CO { A = 1.02E+08 n = 1.66 E = 2.75 }
2603    
2604    
2605    
2606     #==========================================================================#
2607     # #
2608     # Napthalene Oxidation Chemistry #
2609     # Adapted from Benzene #
2610     # #
2611     #==========================================================================#
2612    
2613     # Naphthalene
2614     # 5/3 of the rate for A1
2615     # ----------------------
2616    
2617     NP01f: A2-C10H8 -> A2--C10H7 + H { A = 8.60E+60 n =-12.48 E = 619.55 }
2618     NP02f: A2-C10H8 + H -> A2--C10H7 + H2 { A = 4.01E+08 n = 1.80 E = 68.42 }
2619     NP03f: A2-C10H8 + OH -> A2--C10H7 + H2O { A = 3.90E+04 n = 2.68 E = 3.07 }
2620    
2621     NP04f: A2-C10H8 -> A2*-C10H7 + H { A = 8.60E+60 n =-12.48 E = 619.55 }
2622     NP05f: A2-C10H8 + H -> A2*-C10H7 + H2 { A = 4.01E+08 n = 1.80 E = 68.42 }
2623     NP06f: A2-C10H8 + OH -> A2*-C10H7 + H2O { A = 3.90E+04 n = 2.68 E = 3.07 }
2624    
2625     NP07f: A2-C10H8 + O -> A2O-C10H7O + H { A = 3.32E+07 n = 1.80 E = 16.63 }
2626     NP08f: A2-C10H8 + O -> A2OH-C10H8O { A = 2.55E+10 n = 0.92 E = 13.79 }
2627     NP09f: A2-C10H8 + O -> C9H8 + CO { A = 2.55E+17 n = -0.89 E = 64.89 }
2628    
2629     NP10f: A2-C10H8 + OH -> A2OH-C10H8O + H { A = 2.20E+02 n = 3.25 E = 23.39 }
2630    
2631    
2632     # Naphthyl radical
2633     # Full rate for A1-
2634     # -----------------
2635    
2636     # Park, Nguyen, Xu, Lin 2009
2637     NP11f: A2--C10H7 -> A2*-C10H7 { A = 1.51E+07 n = .00 E = 184.85 }
2638    
2639     NP12f: A2--C10H7 + O2 -> A2O-C10H7O + O { A = 8.57E+20 n = -2.27 E = 30.08 }
2640     NP13f: A2*-C10H7 + O2 -> A2O-C10H7O + O { A = 8.57E+20 n = -2.27 E = 30.08 }
2641    
2642     NP14 : A2--C10H7 + O2 -> C9H6O + CO + H { A = 3.00E+13 n = .00 E = 37.58 }
2643     NP15 : A2*-C10H7 + O2 -> C9H6O + CO + H { A = 3.00E+13 n = .00 E = 37.58 }
2644    
2645     NP16f: A2--C10H7 + O -> A2O-C10H7O { A = 1.00E+14 n = .00 E = .00 }
2646     NP17f: A2*-C10H7 + O -> A2O-C10H7O { A = 1.00E+14 n = .00 E = .00 }
2647    
2648     NP18f: A2--C10H7 + OH -> A2O-C10H7O + H { A = 3.00E+13 n = .00 E = .00 }
2649     NP19f: A2*-C10H7 + OH -> A2O-C10H7O + H { A = 3.00E+13 n = .00 E = .00 }
2650    
2651    
2652     # Naphthol
2653     # Full rate for A1OH
2654     # ------------------
2655    
2656     NP20f: A2OH-C10H8O -> C9H8 + CO { A = 8.62E+15 n = -0.61 E = 310.11 }
2657     NP21f: A2OH-C10H8O -> A2O-C10H7O + H { A = 1.01E+71 n =-15.92 E = 522.12 }
2658    
2659     NP22f: A2OH-C10H8O + H -> A2O-C10H7O + H2 { A = 6.83E+01 n = 3.40 E = 30.26 }
2660     NP23f: A2OH-C10H8O + OH -> A2O-C10H7O + H2O { A = 1.73E+01 n = 3.40 E = -4.78 }
2661     NP24f: A2OH-C10H8O + CH3 -> A2O-C10H7O + CH4 { A = 3.70E-04 n = 4.70 E = 20.20 }
2662    
2663    
2664     # Naphthoxy radical
2665     # Full rate for A1O
2666     # -----------------
2667    
2668     NP25f: A2O-C10H7O -> C9H7 + CO { A = 2.90E+10 n = .00 E = 152.40 }
2669     NP26 : A2O-C10H7O + O -> C9H6O + CO + H { A = 1.68E+14 n = .00 E = .00 }
2670     NP27 : A2O-C10H7O + O2 -> C9H6O + CO + OH { A = 6.51E+07 n = 1.30 E = 73.92 }
2671    
2672    
2673    
2674     #=========================================================================#
2675     # #
2676     # alpha-MethylNaphthalene chemistry #
2677     # Adapted from Toluene chemistry #
2678     # #
2679     #=========================================================================#
2680    
2681    
2682     # MethylNaphthalene
2683     # -----------------
2684    
2685     MN01f: A2CH3-C11H10 + H -> A2-C10H8 + CH3 { A = 2.31E+06 n = 2.17 E = 17.42 }
2686     MN02f: A2CH3-C11H10 + OH -> A2OH-C10H8O + CH3 { A = 7.83E+02 n = 2.88 E = 13.48 }
2687    
2688     # Collision Limit at 298K
2689     MN03f: A2CH3-C11H10 -> A2CH2-C11H9 + H { A = 1.25E+18 n = -0.60 E = 396.59 }
2690     MN04f: A2CH3-C11H10 -> A2--C10H7 + CH3 { A = 3.20E+34 n = -5.02 E = 478.03 }
2691    
2692     MN05f: A2CH2-C11H9 + H -> A2--C10H7 + CH3 { A = 5.83E+67 n =-14.15 E = 285.89 }
2693     MN06f: A2CH2-C11H9 -> C9H7 + C2H2 { A = 8.20E+14 n = .00 E = 337.55 }
2694    
2695     MN07f: A2CH3-C11H10 + H -> A2CH2-C11H9 + H2 { A = 6.47E+00 n = 3.98 E = 14.16 }
2696     MN08f: A2CH3-C11H10 + O -> A2CH2-C11H9 + OH { A = 1.18E+00 n = 4.09 E = 10.65 }
2697     MN09f: A2CH3-C11H10 + OH -> A2CH2-C11H9 + H2O { A = 1.77E+05 n = 2.39 E = -2.52 }
2698     MN10f: A2CH3-C11H10 + O2 -> A2CH2-C11H9 + HO2 { A = 2.18E+07 n = 2.50 E = 192.65 }
2699     MN11f: A2CH3-C11H10 + CH3 -> A2CH2-C11H9 + CH4 { A = 1.73E+01 n = 3.44 E = 43.47 }
2700     MN12f: A2CH3-C11H10 + HO2 -> A2CH2-C11H9 + H2O2 { A = 9.33E+04 n = 2.50 E = 61.44 }
2701    
2702     MN13 : A2CH3-C11H10 + O -> A2-C10H8 + CO + 2 H { A = 1.10E+13 n = .00 E = 18.96 }
2703     MN14 : A2CH3-C11H10 + O -> C9H7 + CH3 + CO { A = 1.47E+13 n = .00 E = 18.96 }
2704    
2705    
2706     # Methylene-Naphthyl
2707     # ------------------
2708    
2709     MN15f: A2CH2-C11H9 + O -> A2-C10H8 + HCO { A = 6.98E+12 n = 0.33 E = 2.87 }
2710     MN16f: A2CH2-C11H9 + O -> A2CHO-C11H8O + H { A = 2.75E+13 n = 0.07 E = 3.06 }
2711     MN17f: A2CH2-C11H9 + O2 -> A2CHO-C11H8O + OH { A = 3.76E+15 n = -1.55 E = 47.37 }
2712     MN18f: A2CH2-C11H9 + HO2 -> A2CH2O-C11H9O + OH { A = 1.19E+09 n = 1.03 E = -9.41 }
2713    
2714     MN19 : A2CH2-C11H9 + C3H3 -> A3-C14H10 + 2H { A = 1.88E+38 n = -7.53 E = 99.91 }
2715    
2716    
2717     # Methoxy-Naphthyl
2718     # ----------------
2719    
2720     MN20f: A2CH2O-C11H9O -> A2CHO-C11H8O + H { A = 1.27E+13 n = .00 E = 86.19 }
2721     MN21f: A2CH2O-C11H9O -> A2--C10H7 + CH2O { A = 7.21E+33 n = -6.21 E = 154.18 }
2722    
2723     MN22f: A2CH2O-C11H9O + H -> A2CHO-C11H8O + H2 { A = 1.33E+13 n = .00 E = .00 }
2724     MN23f: A2CH2O-C11H9O + O -> A2CHO-C11H8O + OH { A = 6.67E+12 n = .00 E = .00 }
2725     MN24f: A2CH2O-C11H9O + OH -> A2CHO-C11H8O + H2O { A = 3.33E+12 n = .00 E = .00 }
2726     MN25f: A2CH2O-C11H9O + O2 -> A2CHO-C11H8O + HO2 { A = 4.11E+10 n = .00 E = 7.32 }
2727    
2728    
2729     # Naphthaldehyde
2730     # --------------
2731    
2732     MN26 : A2CHO-C11H8O -> A2--C10H7 + CO + H { A = 2.10E+16 n = .00 E = 342.00 }
2733    
2734     MN27 : A2CHO-C11H8O + H -> A2--C10H7 + CO +H2 { A = 2.05E+09 n = 1.16 E = 10.06 }
2735     MN28 : A2CHO-C11H8O + O -> A2--C10H7 + CO +OH { A = 2.92E+12 n = .00 E = 7.57 }
2736     MN29 : A2CHO-C11H8O + OH -> A2--C10H7 + CO +H2O { A = 2.34E+10 n = 0.73 E = -4.66 }
2737     MN30 : A2CHO-C11H8O + CH3-> A2--C10H7 + CO +CH4 { A = 2.72E+06 n = 1.77 E = 24.77 }
2738    
2739    
2740    
2741     #==========================================================================#
2742     # #
2743     # PAH chemistry #
2744     # HACA Based Mechanism #
2745     # #
2746     #==========================================================================#
2747    
2748     # Fulvene
2749     # -------
2750    
2751     # Jasper & Hansen 2013 - 1atm
2752     P01f: C5H4CH2 + H -> A1-C6H6 + H { A = 1.14E+32 n = -4.88 E = 79.05 }
2753    
2754     # Senosiain & Miller 2007 (JPCA)
2755     P02f: N-C4H5 + C2H2 -> C5H4CH2 + H { A = 4.62E+15 n = -0.89 E = 38.25 }
2756     P03f: I-C4H5 + C2H2 -> C5H4CH2 + H { A = 6.80E+24 n = -3.45 E = 85.09 }
2757    
2758     # Miller & Klippenstein 2003
2759     P04f: C5H4CH2 -> A1-C6H6 { A = 1.45E+45 n = -8.90 E = 405.86 }
2760     P05f: C5H4CH2 -> A1--C6H5 + H { A = 2.24E+68 n =-14.65 E = 596.54 }
2761    
2762    
2763     # Benzene
2764     # -------
2765    
2766     # Wang & Frenklach 1997
2767     P06f: N-C4H3 + C2H2 -> A1--C6H5 { A = 9.60E+70 n =-17.77 E = 130.96 }
2768    
2769     # Senosiain & Miller 2007 (JPCA)
2770     P07f: N-C4H5 + C2H2 -> A1-C6H6 + H { A = 1.38E+16 n = -1.00 E = 37.24 }
2771     P08f: I-C4H5 + C2H2 -> A1-C6H6 + H { A = 1.67E+23 n = -3.30 E = 104.43 }
2772    
2773     # Miller, Klippenstein, Georgievskii, Harding, Allen, Simmonett 2010
2774     P09 : A-C3H5 + C3H3 -> C5H4CH2 + 2H { A = 1.88E+38 n = -7.53 E = 99.91 }
2775    
2776     # Georgievskii, Miller, & Klippenstein 2007
2777     # -> Total rate at 1bar
2778     # Miller & Klippenstein 2003
2779     # -> Branching ratios
2780     # -> 2-ethynyl-1,3-butadiene lumped into Fulvene
2781     # Fitted rates valid for 800K-2000K - P=1bar
2782     P10f: C3H3 + C3H3 -> C5H4CH2 { A = 8.25E+46 n =-10.10 E = 70.96 }
2783     P11f: C3H3 + C3H3 -> A1-C6H6 { A = 1.07E+45 n = -9.57 E = 71.19 }
2784     P12f: C3H3 + C3H3 -> A1--C6H5 + H { A = 5.77E+37 n = -7.00 E = 131.82 }
2785    
2786     # Tokmakov & Lin 2004
2787     P13f: A1--C6H5 + C2H4 -> A1-C6H6 + C2H3 { A = 9.45E-03 n = 4.47 E = 18.71 }
2788    
2789    
2790     # Naphthalene
2791     # -----------
2792    
2793     # From A1 (x1/3)
2794     P14f: A1C2H-C8H6 + C2H -> A2--C10H7 { A = 6.67E+13 n = .00 E = .00 }
2795     P15f: A1C2H3-C8H8 + C2H -> A2-C10H8 + H { A = 6.67E+13 n = .00 E = .00 }
2796    
2797     # Kislov & Mebel 2005
2798     P16f: A1C2H*-C8H5 + C2H2 -> A2--C10H7 { A = 1.34E+04 n = 2.50 E = 5.37 }
2799     P17f: A1C2H2-C8H7 + C2H2 -> A2-C10H8 + H { A = 2.62E+06 n = 2.00 E = 19.16 }
2800     P18f: A1C2H3*-C8H7 + C2H2 -> A2-C10H8 + H { A = 3.02E+03 n = 2.55 E = 13.31 }
2801    
2802     # From A1 (x1/3)
2803     P19f: A1C2H-C8H6 + C2H3 -> A2-C10H8 + H { A = 4.50E+16 n = -1.15 E = 61.01 }
2804    
2805     # From A1-
2806     P20f: A1C2H*-C8H5 + C2H4 -> A2-C10H8 + H { A = 3.62E+28 n = -4.24 E = 99.85 }
2807    
2808     # Aguilera-Iparraguirre & Klopper 2007
2809     # Total entrance channel rate
2810     P21f: A1--C6H5 + C4H4 -> A2-C10H8 + H { A = 1.26E+04 n = 2.61 E = 6.00 }
2811    
2812    
2813     # From A1 (x2/3)
2814     P22f: A2-C10H8 + C2H -> A2C2HA-C12H8 + H { A = 1.67E+14 n = .00 E = .00 }
2815     P23f: A2-C10H8 + C2H -> A2C2HB-C12H8 + H { A = 1.67E+14 n = .00 E = .00 }
2816    
2817     # Park, Nguyen, Xu, Lin 2009
2818     P24f: A2--C10H7 + C2H2 -> A2R5-C12H8 + H { A = 2.81E+07 n = 1.77 E = 9.37 }
2819     P25f: A2*-C10H7 + C2H2 -> A2C2HB-C12H8 + H { A = 5.38E+07 n = 1.65 E = 10.71 }
2820    
2821     # From A1 (x2/3)
2822     P26f: A2-C10H8 + C2H3 -> A2C2H2A-C12H9 + H2 { A = 9.01E+16 n = -1.15 E = 61.01 }
2823     P27f: A2-C10H8 + C2H3 -> A2C2H2B-C12H9 + H2 { A = 9.01E+16 n = -1.15 E = 61.01 }
2824    
2825     # From A1-
2826     P28f: A2--C10H7 + C2H4 -> A2C2H2A-C12H9 + H2 { A = 3.62E+28 n = -4.24 E = 99.85 }
2827     P29f: A2*-C10H7 + C2H4 -> A2C2H2B-C12H9 + H2 { A = 3.62E+28 n = -4.24 E = 99.85 }
2828    
2829    
2830     # From A1C2H2
2831     P30f: A2C2H2A-C12H9 -> A2C2HA-C12H8 + H { A = 1.81E+54 n =-12.69 E = 215.02 }
2832     P31f: A2C2H2A-C12H9 + H -> A2C2HA-C12H8 + H2 { A = 1.50E+13 n = .00 E = .00 }
2833     P32f: A2C2H2A-C12H9 + OH -> A2C2HA-C12H8 + H2O { A = 2.50E+12 n = .00 E = .00 }
2834    
2835     P33f: A2C2H2B-C12H9 -> A2C2HB-C12H8 + H { A = 1.81E+54 n =-12.69 E = 215.02 }
2836     P34f: A2C2H2B-C12H9 + H -> A2C2HB-C12H8 + H2 { A = 1.50E+13 n = .00 E = .00 }
2837     P35f: A2C2H2B-C12H9 + OH -> A2C2HB-C12H8 + H2O { A = 2.50E+12 n = .00 E = .00 }
2838    
2839     # From A1 (x1/6)
2840     P36f: A2C2HA-C12H8 -> A2C2HA*-C12H7 + H { A = 2.15E+60 n =-12.48 E = 619.55 }
2841     P37f: A2C2HA-C12H8 + H -> A2C2HA*-C12H7 + H2 { A = 1.00E+08 n = 1.80 E = 68.42 }
2842     P38f: A2C2HA-C12H8 + OH -> A2C2HA*-C12H7 + H2O { A = 3.90E+03 n = 2.68 E = 3.07 }
2843    
2844     P39f: A2C2HB-C12H8 -> A2C2HB*-C12H7 + H { A = 2.15E+60 n =-12.48 E = 619.55 }
2845     P40f: A2C2HB-C12H8 + H -> A2C2HB*-C12H7 + H2 { A = 1.00E+08 n = 1.80 E = 68.42 }
2846     P41f: A2C2HB-C12H8 + OH -> A2C2HB*-C12H7 + H2O { A = 3.90E+03 n = 2.68 E = 3.07 }
2847    
2848    
2849     # Acenaphthalene
2850     # --------------
2851    
2852     # Kislov & Mebel 2005
2853     P42f: A2C2H2A-C12H9 -> A2R5-C12H8 + H { A = 2.88E+11 n = 0.23 E = 71.24 }
2854    
2855     # Lifshitz, Tambura & Dubnikova 2007
2856     P43f: A2C2HA-C12H8 + H -> A2R5-C12H8 + H { A = 3.52E+12 n = .00 E = 55.90 }
2857    
2858     # From A1 (x2/3)
2859     P44f: A2R5-C12H8 -> A2R5--C12H7 + H { A = 8.60E+60 n =-12.48 E = 619.55 }
2860     P45f: A2R5-C12H8 + H -> A2R5--C12H7 + H2 { A = 4.01E+08 n = 1.80 E = 68.42 }
2861     P46f: A2R5-C12H8 + OH -> A2R5--C12H7 + H2O { A = 1.34E+04 n = 2.68 E = 3.07 }
2862    
2863    
2864     # From A1 (x2/3)
2865     P47f: A2R5-C12H8 + C2H -> A2R5C2H-C14H8 + H { A = 1.67E+14 n = .00 E = .00 }
2866    
2867     # From A2*
2868     P48f: A2R5--C12H7 + C2H2 -> A2R5C2H-C14H8 + H { A = 5.38E+07 n = 1.65 E = 10.71 }
2869    
2870     # From A1 (x2/3)
2871     P49f: A2R5-C12H8 + C2H3 -> A2R5C2H2-C14H9 + H2 { A = 9.01E+16 n = -1.15 E = 61.01 }
2872    
2873     # From A1-
2874     P50f: A2R5--C12H7 + C2H4 -> A2R5C2H2-C14H9 + H2 { A = 3.62E+28 n = -4.24 E = 99.85 }
2875    
2876    
2877     # From A1C2H2
2878     P51f: A2R5C2H2-C14H9 -> A2R5C2H-C14H8 + H { A = 2.09E+38 n = -7.74 E = 196.19 }
2879     P52f: A2R5C2H2-C14H9 + H -> A2R5C2H-C14H8 + H2 { A = 1.65E+11 n = 0.49 E = 44.48 }
2880     P53f: A2R5C2H2-C14H9 + OH-> A2R5C2H-C14H8 + H2O { A = 2.50E+12 n = .00 E = .00 }
2881    
2882     # From A1 (x1/6)
2883     P54f: A2R5C2H-C14H8 -> A2R5C2H*-C14H7 + H { A = 2.15E+60 n =-12.48 E = 619.55 }
2884     P55f: A2R5C2H-C14H8 + H -> A2R5C2H*-C14H7 + H2 { A = 1.00E+08 n = 1.80 E = 68.42 }
2885     P56f: A2R5C2H-C14H8 + OH-> A2R5C2H*-C14H7 + H2O { A = 3.90E+03 n = 2.68 E = 3.07 }
2886    
2887    
2888     # Biphenyl
2889     # --------
2890    
2891    
2892     # Park, Burova,, Rodgers & Lin 1999
2893     # Fitted exp rate
2894     P57f: A1-C6H6 + A1--C6H5 -> P2-C12H10 + H { A = 9.55E+11 n = .00 E = 9.07 }
2895    
2896     # Tranter, Klippenstein, Harding, Giri, Yang, Keifer 2010
2897     P58f: A1--C6H5 + A1--C6H5 -> P2-C12H10 { A = 7.34E+20 n = -2.34 E = 17.26 }
2898     P59f: A1--C6H5 + A1--C6H5 -> P2--C12H9 + H { A = 2.44E+13 n = 0.89 E = 180.66 }
2899    
2900     # From A1 (x2/3)
2901     P60f: P2-C12H10 -> P2--C12H9 + H { A = 8.60E+60 n =-12.48 E = 619.55 }
2902     P61f: P2-C12H10 + H -> P2--C12H9 + H2 { A = 4.01E+08 n = 1.80 E = 68.42 }
2903     P62f: P2-C12H10 + OH -> P2--C12H9 + H2O { A = 1.34E+04 n = 2.68 E = 3.07 }
2904    
2905    
2906     # Phenanthrene
2907     # ------------
2908    
2909    
2910     # From A1C2H3*
2911     P63f: P2--C12H9 + C2H2 -> A3-C14H10 + H { A = 3.02E+03 n = 2.55 E = 13.31 }
2912    
2913     # From P2 (x1/3)
2914     P64f: A1C2H-C8H6 + A1--C6H5 -> A3-C14H10 + H { A = 3.18E+11 n = .00 E = 9.07 }
2915     # From P2 & P2-
2916     P65f: A1C2H*-C8H5 + A1-C6H6 -> A3-C14H10 + H { A = 9.55E+11 n = .00 E = 9.07 }
2917     P66f: A1C2H*-C8H5 + A1--C6H5 -> A3-C14H10 { A = 1.39E+13 n = .00 E = 0.47 }
2918    
2919    
2920     # From A1 (x1/6)
2921     P67f: A2C2HA-C12H8 + C2H -> A3--C14H9 { A = 3.33E+13 n = .00 E = .00 }
2922     P68f: A2C2HB-C12H8 + C2H -> A3--C14H9 { A = 3.33E+13 n = .00 E = .00 }
2923    
2924     # From A1C2H*
2925     P69f: A2C2HA*-C12H7 + C2H2 -> A3*-C14H9 { A = 1.34E+04 n = 2.50 E = 5.37 }
2926     P70f: A2C2HB*-C12H7 + C2H2 -> A3*-C14H9 { A = 1.34E+04 n = 2.50 E = 5.37 }
2927    
2928     # From A1C2H2
2929     P71f: A2C2H2A-C12H9 + C2H2 -> A3-C14H10 + H { A = 2.62E+06 n = 2.00 E = 19.16 }
2930     P72f: A2C2H2B-C12H9 + C2H2 -> A3-C14H10 + H { A = 2.62E+06 n = 2.00 E = 19.16 }
2931    
2932     # From A1 (x1/6)
2933     P73f: A2C2HA-C12H8 + C2H3 -> A3-C14H10 + H { A = 2.25E+16 n = -1.15 E = 61.01 }
2934     P74f: A2C2HB-C12H8 + C2H3 -> A3-C14H10 + H { A = 2.25E+16 n = -1.15 E = 61.01 }
2935    
2936     # From A1-
2937     P75f: A2C2HA*-C12H7 + C2H4 -> A3-C14H10 + H { A = 3.62E+28 n = -4.24 E = 99.85 }
2938     P76f: A2C2HB*-C12H7 + C2H4 -> A3-C14H10 + H { A = 3.62E+28 n = -4.24 E = 99.85 }
2939    
2940     # From A1-
2941     P77f: A2--C10H7 + C4H4 -> A3-C14H10 + H { A = 1.26E+04 n = 2.61 E = 6.00 }
2942     P78f: A2*-C10H7 + C4H4 -> A3-C14H10 + H { A = 1.26E+04 n = 2.61 E = 6.00 }
2943    
2944    
2945     # From A1 (x1/3)
2946     P79f: A3-C14H10 -> A3*-C14H9 + H { A = 4.30E+60 n =-12.48 E = 619.55 }
2947     P80f: A3-C14H10 + H -> A3*-C14H9 + H2 { A = 2.00E+08 n = 1.80 E = 68.42 }
2948     P81f: A3-C14H10 + OH -> A3*-C14H9 + H2O { A = 7.80E+03 n = 2.68 E = 3.07 }
2949    
2950     # From A1 (x2/3)
2951     P82f: A3-C14H10 -> A3--C14H9 + H { A = 8.60E+60 n =-12.48 E = 619.55 }
2952     P83f: A3-C14H10 + H -> A3--C14H9 + H2 { A = 4.01E+08 n = 1.80 E = 68.42 }
2953     P84f: A3-C14H10 + OH -> A3--C14H9 + H2O { A = 1.56E+04 n = 2.68 E = 3.07 }
2954    
2955     # Frenklach 2005
2956     P85f: A3*-C14H9 -> A2R5--C12H7 + C2H2 { A = 1.30E+11 n = 1.08 E = 294.55 }
2957    
2958    
2959     # Acephenanthrylene
2960     # -----------------
2961    
2962    
2963     # From A1C2H*
2964     P86f: A2R5C2H*-C14H7 + C2H2 -> A3R5--C16H9 { A = 1.34E+04 n = 2.50 E = 5.37 }
2965    
2966     # From A1C2H2
2967     P87f: A2R5C2H2-C14H9 + C2H2 -> A3R5-C16H10 + H { A = 2.62E+06 n = 2.00 E = 19.16 }
2968    
2969     # From A2-
2970     P88f: A3--C14H9 + C2H2 -> A3R5-C16H10 + H { A = 2.81E+07 n = 1.77 E = 9.37 }
2971    
2972     # From A1-
2973     P89f: A2R5--C12H7 + C4H4 -> A3R5-C16H10 + H { A = 1.26E+04 n = 2.61 E = 6.00 }
2974    
2975    
2976     # From A1 (x1/3)
2977     P90f: A3R5-C16H10 -> A3R5--C16H9 + H { A = 2.15E+60 n =-12.48 E = 619.55 }
2978     P91f: A3R5-C16H10 + H -> A3R5--C16H9 + H2 { A = 2.01E+08 n = 1.80 E = 68.42 }
2979     P92f: A3R5-C16H10 + OH -> A3R5--C16H9 + H2O { A = 7.80E+03 n = 2.68 E = 3.07 }
2980    
2981    
2982     # Pyrene
2983     # ------
2984    
2985    
2986     # From A2*
2987     P93f: A3*-C14H9 + C2H2 -> A4-C16H10 + H { A = 5.38E+07 n = 1.65 E = 10.71 }
2988    
2989     # From A1 (x4/3)
2990     P94f: A4-C16H10 -> A4--C16H9 + H { A = 1.72E+60 n =-12.48 E = 619.55 }
2991     P95f: A4-C16H10 + H -> A4--C16H9 + H2 { A = 8.03E+08 n = 1.80 E = 68.42 }
2992     P96f: A4-C16H10 + OH -> A4--C16H9 + H2O { A = 3.12E+04 n = 2.68 E = 3.07 }
2993    
2994    
2995     # Cyclopenta[cd]pyrene
2996     # --------------------
2997    
2998    
2999     # From A2-/A2*
3000     P97f: A4--C16H9 + C2H2 -> A4R5-C18H10 + H { A = 2.81E+07 n = 1.77 E = 9.37 }
3001     P98f: A3R5--C16H9 + C2H2 -> A4R5-C18H10 + H { A = 5.38E+07 n = 1.65 E = 10.71 }
3002    
3003    
3004     # Fluoranthene
3005     # ------------
3006    
3007    
3008     # From A1+A1- (x2/3 and x1)
3009     P99 : A2-C10H8 + A1--C6H5 -> FLTN-C16H10 + H2+H { A = 6.37E+11 n = .00 E = 9.07 }
3010     P100: A2--C10H7 + A1-C6H6 -> FLTN-C16H10 + H2+H { A = 9.55E+11 n = .00 E = 9.07 }
3011    
3012     # From A1-+A1-
3013     P101: A2--C10H7 + A1--C6H5 -> FLTN-C16H10 + 2H { A = 1.39E+13 n = .00 E = 0.47 }
3014    
3015    
3016    
3017     #==========================================================================#
3018     # #
3019     # Higher PAH Oxidation Chemistry #
3020     # Adapted from Benzene #
3021     # #
3022     #==========================================================================#
3023    
3024     # From A1-+O2
3025     OX01 : A3*-C14H9 + O2 -> A2C2H2B-C12H9 + 2CO { A = 8.57E+20 n = -2.27 E = 30.08 }
3026     OX02 : A3--C14H9 + O2 -> A2C2H2A-C12H9 + 2CO { A = 8.57E+20 n = -2.27 E = 30.08 }
3027     OX03 : A4--C16H9 + O2 -> A3*-C14H9 + 2CO { A = 8.57E+20 n = -2.27 E = 30.08 }
3028     OX04 : A2R5--C12H7 + O2 -> A2--C10H7 + 2CO { A = 8.57E+20 n = -2.27 E = 30.08 }
3029     OX05 : A3R5--C16H9 + O2 -> A3*-C14H9 + 2CO { A = 8.57E+20 n = -2.27 E = 30.08 }
3030    
3031     # From A1+OH
3032     # Rescaled by number of active sites
3033     OX06 : A3-C14H10 + OH -> A2C2HA-C12H8 +CH3+CO { A = 1.10E+02 n = 3.25 E = 23.39 }
3034     OX07 : A3-C14H10 + OH -> A2C2HB-C12H8 +CH3+CO { A = 1.10E+02 n = 3.25 E = 23.39 }
3035     OX08 : A4-C16H10 + OH -> A3-C14H10 + HCCO { A = 2.20E+02 n = 3.25 E = 23.39 }
3036     OX09 : A2R5-C12H8 + OH -> A2-C10H8 + HCCO { A = 1.76E+02 n = 3.25 E = 23.39 }
3037     OX10 : A3R5-C16H10 + OH -> A3-C14H10 + HCCO { A = 2.20E+02 n = 3.25 E = 23.39 }
3038     OX11 : A4R5-C18H10 + OH -> A4-C16H10 + HCCO { A = 2.20E+02 n = 3.25 E = 23.39 }
3039     OX12 : FLTN-C16H10 + OH -> A3-C14H10 + HCCO { A = 2.20E+02 n = 3.25 E = 23.39 }
3040    
3041    
3042    
3043     #================================================================#
3044     # #
3045     # Soot Formation #
3046     # #
3047     #================================================================#
3048    
3049     ###### H-Abstraction ######
3050    
3051     # Tokmakov & Lin 1999/2002
3052     # Rates indep of pressure
3053     # 1/6 of forward and full backward
3054     SOOT1f: Soot-CH + OH -> Soot-C + H2O { A = 6.72E+01 n = 3.33 E = 6.09 }
3055     SOOT1b: Soot-C + H2O -> Soot-CH + OH { A = 6.44E-01 n = 3.79 E = 27.96 }
3056    
3057     # Mebel & Lin 1997
3058     # Rates indep of pressure
3059     # 1/6 of forward and full backward
3060     SOOT2f: Soot-CH + H -> Soot-C + H2 { A = 1.00E+08 n = 1.80 E = 68.42 }
3061     SOOT2b: Soot-C + H2 -> Soot-CH + H { A = 8.68E+04 n = 2.36 E = 25.46 }
3062    
3063     # Harding, Georgievskii & Klippenstein 2005
3064     # High Pressure Limit
3065     # 1/6 of forward and full backward
3066     SOOT3f: Soot-CH -> Soot-C + H { A = 1.13E+16 n = -0.06 E = 476.05 }
3067     SOOT3b: Soot-C + H -> Soot-CH { A = 4.17E+13 n = 0.15 E = .00 }
3068    
3069    
3070     ###### C2H2-Addition ######
3071    
3072     # Tokmakov & Lin 2004
3073     # High pressure rates for A1- + C2H2 <=> A1C2H2 (x2)
3074     SOOT4: Soot-C + C2H2 -> Soot-CH noCheck { A = 2.52E+09 n = 1.10 E = 17.13 }
3075    
3076    
3077     ###### Oxidation ######
3078    
3079     # Assume first reaction step is the limiting step:
3080     # Attack by O2 or OH
3081    
3082     # Kazakov, Wang & Frenklach 1995
3083     SOOT5: Soot-C + O2 -> Soot-C + 2CO noCheck { A = 2.20E+12 n = .00 E = 31.38 }
3084    
3085     # Sarofim 1981
3086     # Directly Coded in FlameMaster
3087     # From collision efficiency - 0.13
3088     SOOT6 : Soot-CH + OH -> Soot-C + CO noCheck { A = 0.00E+00 n = .00 E = .00 }
3089    
3090    
3091     # **** Third Body *****
3092    
3093     Let M0 = 1.0 [OTHER].
3094    
3095     Let M1 = 0.0 [H2] + 0.0 [H2O] + 0.63 [AR] + 0.00 [CO2] + 1.0 [OTHER].
3096     Let M2 = 2.5 [H2] + 12.0 [H2O] + 0.75 [AR] + 1.0 [OTHER].
3097     Let M3 = 2.5 [H2] + 12.0 [H2O] + 0.00 [AR] + 1.0 [OTHER].
3098     Let M4 = 1.5 [H2] + 11.7 [H2O] + 0.52 [AR] + 1.09 [CO] + 2.18 [CO2] + 0.89 [O2] + 1.0 [OTHER].
3099     Let M5 = 3.0 [H2] + 0.0 [H2O] + 2.00 [N2] + 1.50 [O2] + 1.0 [OTHER].
3100     Let M6 = 2.5 [H2] + 9.0 [H2O] + 1.50 [N2] + 1.0 [OTHER].
3101    
3102     Let M7 = 2.0 [H2] + 12.0 [H2O] + 0.70 [AR] + 1.75 [CO] + 3.60 [CO2] + 1.0 [OTHER].
3103     Let M8 = 2.0 [H2] + 0.0 [H2O] + 1.75 [CO] + 3.60 [CO2] + 1.0 [OTHER].
3104    
3105     Let M9 = 2.0 [H2] + 6.0 [H2O] + 0.70 [AR] + 1.50 [CO] + 2.00 [CO2] + 2 [CH4] + 3 [C2H6] + 1.0 [OTHER].
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