Let allowed atoms be C, H, O, N, AR. Let additional species be N2. Let temperature exponent be n_k. Let order of reaction be n. Let units for A be [ cm^(3(n-1)) / ( s * mole^(n-1) * K^n_k ) ]. Let units for E be [ kJ / mole ]. Let symbol for soot be SOOT. #=========================================================================# # # # H2/CO Chemistry from # # # # "An optimized kinetic model of H2/CO combustion" # # Davis, Joshi, Wang, and Egolfopoulos # # Proc. Comb. Inst. 30 (2005) 1283-1292 # # # #=========================================================================# # Reactions of H2/O2 1f: H + O2 -> O + OH { A = 2.64E+16 n = -0.67 E = 71.30 } 2f: O + H2 -> H + OH { A = 4.59E+04 n = 2.70 E = 26.19 } 3f: OH + H2 -> H + H2O { A = 1.73E+08 n = 1.51 E = 14.35 } 4f: OH + OH -> O + H2O { A = 3.97E+04 n = 2.40 E = -8.83 } 5f: 2 H + M1 -> H2 + M1 { A = 1.78E+18 n = -1.00 E = .00 } 6f: 2 H + H2 -> H2 + H2 { A = 9.00E+16 n = -0.60 E = .00 } 7f: 2 H + H2O -> H2 + H2O { A = 5.62E+19 n = -1.25 E = .00 } 8f: 2 H + CO2 -> H2 + CO2 { A = 5.50E+20 n = -2.00 E = .00 } 9f: H + OH + M2 -> H2O + M2 { A = 4.40E+22 n = -2.00 E = .00 } 10f: H + O + M3 -> OH + M3 { A = 9.43E+18 n = -1.00 E = .00 } 11f: O + O + M4 -> O2 + M4 { A = 1.20E+17 n = -1.00 E = .00 } 12f: H + O2 + M5 -> HO2 + M5 { Ai= 5.12E+12 ni= 0.44 Ei= .00 A = 6.33E+19 n = -1.40 E = .00 fca = 0.5 fcta = 1.0E-10 fcb = 0.5 fctb = 1.0E+10 } 13f: H2 + O2 -> HO2 + H { A = 5.92E+05 n = 2.43 E = 223.85 } 14f: 2 OH + M6 -> H2O2 + M6 { A = 2.01E+17 n = -0.58 E = -9.59 Ai= 1.11E+14 ni= -0.37 Ei= .00 fcA = 0.2654 fctA = 94 fcb = 0.7346 fctb = 1756 fcc = 1.0 fctc = 5182 } # Reactions of HO2 15f: HO2 + H -> O + H2O { A = 3.97E+12 n = .00 E = 2.81 } 16f: HO2 + H -> OH + OH { A = 7.49E+13 n = .00 E = 1.23 } 17f: HO2 + O -> OH + O2 { A = 4.00E+13 n = .00 E = .00 } # Baulch et al. 1994 # Hong, Vasu, Davidson, Hanson 2010 18f: HO2 + OH -> H2O + O2 { A = 2.89E+13 n = .00 E = -2.10 } 20f: HO2 + HO2 -> O2 + H2O2 { A = 1.30E+11 n = .00 E = -6.82 } 21f: HO2 + HO2 -> O2 + H2O2 { A = 3.66E+14 n = .00 E = 50.21 } # Reactions of H2O2 22f: H2O2 + H -> HO2 + H2 { A = 6.05E+06 n = 2.00 E = 21.76 } 23f: H2O2 + H -> H2O + OH { A = 2.41E+13 n = .00 E = 16.61 } 24f: H2O2 + O -> HO2 + OH { A = 9.63E+06 n = 2.00 E = 16.61 } # Hong, Cook, Davidson, Hanson 2010 25f: H2O2 + OH -> HO2 + H2O { A = 1.74E+12 n = .00 E = 1.33 } 26f: H2O2 + OH -> HO2 + H2O { A = 7.59E+13 n = .00 E = 29.77 } # Reactions of CO/CO2 27f: CO + O + M7 -> CO2 + M7 { A = 1.17E+24 n = -2.79 E = 17.54 Ai= 1.36E+10 ni= .00 Ei= 9.97 fcc = 1.0 fctc = 0.0 } 28f: CO + OH -> CO2 + H { A = 8.00E+11 n = 0.14 E = 30.76 } 29f: CO + OH -> CO2 + H { A = 8.78E+10 n = 0.03 E = -0.07 } 30f: CO + O2 -> CO2 + O { A = 1.12E+12 n = .00 E = 199.58 } 31f: CO + HO2 -> CO2 + OH { A = 3.01E+13 n = .00 E = 96.23 } # Reactions of HCO 32f: HCO + H -> CO + H2 { A = 1.20E+14 n = .00 E = .00 } 33f: HCO + O -> CO + OH { A = 3.00E+13 n = .00 E = .00 } 34f: HCO + O -> CO2 + H { A = 3.00E+13 n = .00 E = .00 } 35f: HCO + OH -> CO + H2O { A = 3.02E+13 n = .00 E = .00 } 36f: HCO + M8 -> CO + H + M8 { A = 1.87E+17 n = -1.00 E = 71.13 } 37f: HCO + H2O -> CO + H + H2O { A = 2.24E+18 n = -1.00 E = 71.13 } # New fit to experimental data # Colbergs & Friedrichs 2006 38f: HCO + O2 -> CO + HO2 { A = 5.31E+10 n = 0.69 E = -0.52 } #=========================================================================# # # # C1 and C2 chemistry is taken from # # # # GRI-MECH version 3.0 # # http://www.me.berkeley.edu/gri_mech/ # # # # Gregory P. Smith, David M. Golden, Michael Frenklach, Nigel W. Moriarty # # Boris Eiteneer, Mikhail Goldenberg, C. Thomas Bowman, Ronald K. Hanson, # # Soonho Song, William C. Gardiner, Jr., Vitali V. Lissianski, Zhiwei Qin # # # #=========================================================================# # Reactions of C G01f: C + OH -> CO + H { A = 5.00E+13 n = .00 E = .00 } G02f: C + O2 -> CO + O { A = 5.80E+13 n = .00 E = 2.41 } # Reactions of CH G03f: CH + H -> C + H2 { A = 1.65E+14 n = .00 E = .00 } G04f: CH + O -> CO + H { A = 5.70E+13 n = .00 E = .00 } G05f: CH + OH -> HCO + H { A = 3.00E+13 n = .00 E = .00 } G06f: CH + H2 -> T-CH2 + H { A = 1.08E+14 n = .00 E = 13.01 } G07f: CH + H2 + M9 -> CH3 + M9 { A = 4.82E+25 n = -2.80 E = 2.47 Ai= 1.97E+12 ni= 0.43 Ei= -1.55 fcA = 0.422 fctA = 122 fcb = 0.578 fctb = 2535 fcc = 1.0 fctc = 9365 } G08f: CH + H2O -> CH2O + H { A = 5.71E+12 n = .00 E = -3.16 } G09f: CH + O2 -> HCO + O { A = 6.71E+13 n = .00 E = .00 } G10f: CH + CO + M9 -> HCCO + M9 { A = 2.69E+28 n = -3.74 E = 8.10 Ai= 5.00E+13 ni= .00 Ei= .00 fcA = 0.4243 fctA = 237 fcb = 0.5757 fctb = 1652 fcc = 1.0 fctc = 5069 } G11f: CH + CO2 -> HCO + CO { A = 1.90E+14 n = .00 E = 66.07 } # Reactions of CO/HCO G12f: CO + H2 + M9 -> CH2O + M9 { A = 5.07E+27 n = -3.42 E = 352.92 Ai= 4.30E+07 ni= 1.50 Ei= 333.05 fcA = 0.068 fctA = 197 fcb = 0.932 fctb = 1540 fcc = 1.0 fctc = 10300 } G13f: HCO + H + M9 -> CH2O + M9 { A = 2.47E+24 n = -2.57 E = 1.78 Ai= 1.09E+12 ni= .48 Ei= -1.09 fcA = 0.2176 fctA = 271 fcb = 0.7824 fctb = 2755 fcc = 1.0 fctc = 6570 } # Reactions T-CH2 (triplet) G14f: T-CH2 + H + M9 -> CH3 + M9 { A = 1.04E+26 n = -2.76 E = 6.69 Ai= 6.00E+14 ni= .00 Ei= .00 fcA = 0.438 fctA = 91 fcb = 0.562 fctb = 5836 fcc = 1.0 fctc = 8552 } G15f: T-CH2 + O -> HCO + H { A = 8.00E+13 n = .00 E = .00 } G16f: T-CH2 + OH -> CH2O + H { A = 2.00E+13 n = .00 E = .00 } G17f: T-CH2 + OH -> CH + H2O { A = 1.13E+07 n = 2.00 E = 12.55 } G18f: T-CH2 + H2 -> H + CH3 { A = 5.00E+05 n = 2.00 E = 30.25 } G19: T-CH2 + O2 -> CO2 + 2 H { A = 5.80E+12 n = .00 E = 6.28 } G20f: T-CH2 + O2 -> CH2O + O { A = 2.40E+12 n = .00 E = 6.28 } G21: T-CH2 + O2 -> OH + H + CO { A = 5.00E+12 n = .00 E = 6.28 } G22f: T-CH2 + HO2 -> CH2O + OH { A = 2.00E+13 n = .00 E = .00 } G23f: T-CH2 + C -> C2H + H { A = 5.00E+13 n = .00 E = .00 } G24f: T-CH2 + CO + M9 -> CH2CO + M9 { A = 2.69E+33 n = -5.11 E = 29.69 Ai= 8.10E+11 ni= .50 Ei= 18.87 fcA = 0.4093 fctA = 275 fcb = 0.5907 fctb = 1226 fcc = 1.0 fctc = 5185 } G25f: T-CH2 + CH -> C2H2 + H { A = 4.00E+13 n = .00 E = .00 } G26f: 2 T-CH2 -> C2H2 + H2 { A = 1.60E+15 n = .00 E = 49.97 } G27: 2 T-CH2 -> C2H2 + 2 H { A = 2.00E+14 n = .00 E = 45.98 } # Reactions of S-CH2 (singlet) G28f: S-CH2 + N2 -> T-CH2 + N2 { A = 1.50E+13 n = .00 E = 2.51 } G29f: S-CH2 + AR -> T-CH2 + AR { A = 9.00E+12 n = .00 E = 2.51 } G30f: S-CH2 + H -> CH + H2 { A = 3.00E+13 n = .00 E = .00 } G31f: S-CH2 + O -> CO + H2 { A = 1.50E+13 n = .00 E = .00 } G32f: S-CH2 + O -> HCO + H { A = 1.50E+13 n = .00 E = .00 } G33f: S-CH2 + OH -> CH2O + H { A = 3.00E+13 n = .00 E = .00 } G34f: S-CH2 + H2 -> CH3 + H { A = 7.00E+13 n = .00 E = .00 } G35f: S-CH2 + O2 -> H + OH + CO { A = 2.80E+13 n = .00 E = .00 } G36f: S-CH2 + O2 -> CO + H2O { A = 1.20E+13 n = .00 E = .00 } G37f: S-CH2 + H2O + M9 -> CH3OH + M9 { A = 1.88E+38 n = -6.36 E = 21.09 Ai= 4.82E+17 ni= -1.16 Ei= 4.79 fcA = 0.3973 fctA = 208 fcb = 0.6027 fctb = 3922 fcc = 1.0 fctc = 10180 } G38f: S-CH2 + H2O -> T-CH2 + H2O { A = 3.00E+13 n = .00 E = .00 } G39: S-CH2 + H2O -> H2 + CH2O { A = 6.82E+10 n = .25 E = -3.91 } G40f: S-CH2 + CO -> T-CH2 + CO { A = 9.00E+12 n = .00 E = .00 } G41f: S-CH2 + CO2 -> T-CH2 + CO2 { A = 7.00E+12 n = .00 E = .00 } G42f: S-CH2 + CO2 -> CH2O + CO { A = 1.40E+13 n = .00 E = .00 } # Reactions of CH2O G43f: CH2O + H + M9 -> CH2OH + M9 { A = 1.27E+32 n = -4.82 E = 27.32 Ai= 5.40E+11 ni= .45 Ei= 15.06 fcA = 0.2813 fctA = 103 fcb = 0.7187 fctb = 1291 fcc = 1.0 fctc = 4160 } G44f: CH2O + H + M9 -> CH3O + M9 { A = 2.20E+30 n = -4.80 E = 23.26 Ai= 5.40E+11 ni= .45 Ei= 10.88 fcA = 0.242 fctA = 94 fcb = 0.758 fctb = 1555 fcc = 1.0 fctc = 4200 } G45f: CH2O + H -> HCO + H2 { A = 5.74E+07 n = 1.90 E = 11.47 } G46f: CH2O + O -> HCO + OH { A = 3.90E+13 n = .00 E = 14.81 } G47f: CH2O + OH -> HCO + H2O { A = 3.43E+09 n = 1.18 E = -1.87 } G48f: CH2O + O2 -> HCO + HO2 { A = 1.00E+14 n = .00 E = 167.36 } G49f: CH2O + HO2 -> HCO + H2O2 { A = 5.60E+06 n = 2.00 E = 50.21 } G50f: CH2O + CH -> CH2CO + H { A = 9.46E+13 n = .00 E = -2.16 } # Reactions of CH3 # Zero Pressure: New fit to experimental data # High Pressure: Harding et al. 2005 # Fall off: As in GRI-Mech 3.0 G51f: CH3 + H + M9 -> CH4 + M9 { A = 3.47E+38 n = -6.30 E = 21.23 Ai= 6.92E+13 ni= 0.18 Ei= .00 fcA = 0.217 fctA = 74 fcb = 0.783 fctb = 2941 fcc = 1.0 fctc = 6964 } G52f: CH3 + O -> CH2O + H { A = 5.06E+13 n = .00 E = .00 } G53: CH3 + O -> H + H2 + CO { A = 3.37E+13 n = .00 E = .00 } G54f: CH3 + OH + M9 -> CH3OH + M9 { A = 4.00E+36 n = -5.92 E = 13.14 Ai= 2.79E+18 ni= -1.43 Ei= 5.57 fcA = 0.588 fctA = 195 fcb = 0.412 fctb = 5900 fcc = 1.0 fctc = 6394 } G55f: CH3 + OH -> T-CH2 + H2O { A = 5.60E+07 n = 1.60 E = 22.68 } G56: CH3 + OH -> H2 + CH2O { A = 8.00E+09 n = .00 E = -7.34 } G57f: CH3 + OH -> S-CH2 + H2O { A = 6.44E+17 n = -1.34 E = 5.93 } # Petersen et al. 2007 G58f: CH3 + O2 -> CH3O + O { A = 1.38E+13 n = .00 E = 127.70 } G59f: CH3 + O2 -> CH2O + OH { A = 5.87E+11 n = .00 E = 57.91 } G60f: CH3 + O2 + M0 -> CH3O2 + M0 { A = 3.82E+31 n = -4.89 E = 14.36 Ai= 1.01E+08 ni= 1.63 Ei= .00 fca = 0.955 fcta = 880.1 fcb = 0.045 fctb = 2.5E+9 fcc = 1 fctc = 1.786E+09 } G61f: CH3O2 + CH3 -> CH3O + CH3O { A = 1.00E+13 n = .00 E = -5.02 } G62 : CH3O2 + CH3O2 -> CH3O + CH3O + O2 { A = 1.40E+16 n = -1.61 E = 7.78 } G63 : CH3O2 + HO2 -> CH3O + OH + O2 { A = 2.47E+11 n = .00 E = -6.57 } G64 : CH3O2 + CH2O -> CH3O + OH + HCO { A = 1.99E+12 n = .00 E = 48.83 } G65f: CH3 + HO2 -> CH3O + OH { A = 1.00E+13 n = .00 E = .00 } G66f: CH3 + HO2 -> CH4 + O2 { A = 3.61E+12 n = .00 E = .00 } G67f: CH3 + H2O2 -> CH4 + HO2 { A = 2.45E+04 n = 2.47 E = 21.67 } G68f: CH3 + C -> C2H2 + H { A = 5.00E+13 n = .00 E = .00 } G69f: CH3 + CH -> C2H3 + H { A = 3.00E+13 n = .00 E = .00 } G70f: CH3 + HCO -> CH4 + CO { A = 2.65E+13 n = .00 E = .00 } G71f: CH3 + CH2O -> CH4 + HCO { A = 3.32E+03 n = 2.81 E = 24.52 } G72f: CH3 + T-CH2 -> C2H4 + H { A = 1.00E+14 n = .00 E = .00 } G73f: CH3 + S-CH2 -> C2H4 + H { A = 1.20E+13 n = .00 E = -2.39 } G74f: 2 CH3 -> C2H5 + H { A = 6.84E+12 n = 0.10 E = 44.35 } # Reactions of CH3O/CH2OH G75f: CH3O + H + M9 -> CH3OH + M9 { A = 4.66E+41 n = -7.44 E = 58.91 Ai= 2.43E+12 ni= .52 Ei= 0.21 fcA = 0.30 fctA = 100 fcb = 0.70 fctb = 90000 fcc = 1.0 fctc = 10000 } G76f: CH3O + H -> CH2OH + H { A = 4.15E+07 n = 1.63 E = 8.05 } G77f: CH3O + H -> CH2O + H2 { A = 2.00E+13 n = .00 E = .00 } G78f: CH3O + H -> CH3 + OH { A = 1.50E+12 n = .50 E = -0.46 } G79f: CH3O + H -> S-CH2 + H2O { A = 2.62E+14 n = -0.23 E = 4.48 } G80f: CH3O + O -> CH2O + OH { A = 1.00E+13 n = .00 E = .00 } G81f: CH3O + OH -> CH2O + H2O { A = 5.00E+12 n = .00 E = .00 } G82f: CH3O + O2 -> CH2O + HO2 { A = 4.28E-13 n = 7.60 E = -14.77 } G83f: CH2OH + H + M9 -> CH3OH + M9 { A = 4.36E+31 n = -4.65 E = 21.26 Ai= 1.06E+12 ni= .50 Ei= 0.36 fcA = 0.400 fctA = 100 fcb = 0.600 fctb = 9000 fcc = 1.0 fctc = 10000 } G84f: CH2OH + H -> CH2O + H2 { A = 2.00E+13 n = .00 E = .00 } G85f: CH2OH + H -> CH3 + OH { A = 1.65E+11 n = .65 E = -1.19 } G86f: CH2OH + H -> S-CH2 + H2O { A = 3.28E+13 n = -0.09 E = 2.55 } G87f: CH2OH + O -> CH2O + OH { A = 1.00E+13 n = .00 E = .00 } G88f: CH2OH + OH -> CH2O + H2O { A = 5.00E+12 n = .00 E = .00 } G89f: CH2OH + O2 -> CH2O + HO2 { A = 1.80E+13 n = .00 E = 3.77 } # Reactions of CH4 G90f: CH4 + H -> CH3 + H2 { A = 6.60E+08 n = 1.62 E = 45.36 } G91f: CH4 + O -> CH3 + OH { A = 1.02E+09 n = 1.50 E = 35.98 } G92f: CH4 + OH -> CH3 + H2O { A = 1.00E+08 n = 1.60 E = 13.05 } G93f: CH4 + CH -> C2H4 + H { A = 6.00E+13 n = .00 E = .00 } G94f: CH4 + T-CH2 -> 2 CH3 { A = 2.46E+06 n = 2.00 E = 34.60 } G95f: CH4 + S-CH2 -> 2 CH3 { A = 1.60E+13 n = .00 E = -2.39 } # Reactions of CH3OH G96f: CH3OH + H -> CH2OH + H2 { A = 1.70E+07 n = 2.10 E = 20.38 } G97f: CH3OH + H -> CH3O + H2 { A = 4.20E+06 n = 2.10 E = 20.38 } G98f: CH3OH + O -> CH2OH + OH { A = 3.88E+05 n = 2.50 E = 12.97 } G99f: CH3OH + O -> CH3O + OH { A = 1.30E+05 n = 2.50 E = 20.92 } G100f: CH3OH + OH -> CH2OH + H2O { A = 1.44E+06 n = 2.00 E = -3.52 } G101f: CH3OH + OH -> CH3O + H2O { A = 6.30E+06 n = 2.00 E = 6.28 } G102f: CH3OH + CH3 -> CH2OH + CH4 { A = 3.00E+07 n = 1.50 E = 41.59 } G103f: CH3OH + CH3 -> CH3O + CH4 { A = 1.00E+07 n = 1.50 E = 41.59 } # Reactions of C2H G104f: C2H + H + M9 -> C2H2 + M9 { A = 2.60E+33 n = -4.80 E = 7.95 Ai= 1.00E+17 ni= -1.00 Ei= .00 fcA = 0.3536 fctA = 132 fcb = 0.6464 fctb = 1315 fcc = 1.0 fctc = 5566 } G105f: C2H + O -> CH + CO { A = 5.00E+13 n = .00 E = .00 } G106f: C2H + OH -> H + HCCO { A = 2.00E+13 n = .00 E = .00 } G107f: C2H + O2 -> HCO + CO { A = 1.00E+13 n = .00 E = -3.16 } # New fit to experiment G108f: C2H + H2 -> C2H2 + H { A = 3.31E+06 n = 2.26 E = 3.77 } # Reactions of HCCO G109f: HCCO + H -> S-CH2 + CO { A = 1.00E+14 n = .00 E = .00 } G110f: HCCO + O -> H + 2 CO { A = 1.00E+14 n = .00 E = .00 } # Eiteneer & Frenklach 2003 G111f: HCCO + O2 -> OH + 2 CO { A = 4.20E+10 n = .00 E = 3.57 } G112f: HCCO + CH -> C2H2 + CO { A = 5.00E+13 n = .00 E = .00 } G113f: HCCO + T-CH2 -> C2H3 + CO { A = 3.00E+13 n = .00 E = .00 } G114f: 2 HCCO -> C2H2 + 2 CO { A = 1.00E+13 n = .00 E = .00 } # Reactions of C2H2 # Miller & Klippenstein 2004 G115f: C2H2 + H + M9 -> C2H3 + M9 { A = 6.34E+31 n = -4.66 E = 15.82 Ai= 1.71E+10 ni= 1.27 Ei= 11.33 fcA = 0.2122 fctA =-10212 fcb = 0.00 fctb = 1 fcc = 0.00 fctc = 1 } # Eiteneer & Frenklach 2003 G116f: C2H2 + O -> HCCO + H { A = 8.10E+06 n = 2.00 E = 7.95 } G117f: C2H2 + O -> T-CH2 + CO { A = 1.25E+07 n = 2.00 E = 7.95 } # Tsang & Hampson 1986 # Modified for Collision Limit G118f: C2H + OH -> C2H2 + O { A = 1.81E+13 n = .00 E = .00 } # Senosiain, Klippenstein & Miller 2005 G119f: C2H2 + OH -> C2H + H2O { A = 2.63E+06 n = 2.14 E = 71.38 } G120f: C2H2 + OH -> HCCOH + H { A = 2.41E+06 n = 2.00 E = 53.19 } G121f: C2H2 + OH -> CH2CO + H { A = 7.53E+06 n = 1.55 E = 8.81 } G122f: C2H2 + OH -> CH3 + CO { A = 1.28E+09 n = 0.73 E = 10.79 } # Reactions of CH2CO/HCCOH G123f: CH2CO + H -> HCCO + H2 { A = 5.00E+13 n = .00 E = 33.47 } # Lee & Bozzelli 2002 G124f: CH2CO + H -> CH3 + CO { A = 1.50E+09 n = 1.38 E = 2.57 } G125f: CH2CO + O -> HCCO + OH { A = 1.00E+13 n = .00 E = 33.47 } G126f: CH2CO + O -> T-CH2 + CO2 { A = 1.75E+12 n = .00 E = 5.65 } G127f: CH2CO + OH -> HCCO + H2O { A = 7.50E+12 n = .00 E = 8.37 } G128f: HCCOH + H -> CH2CO + H { A = 1.00E+13 n = .00 E = .00 } # Reactions of C2H3 G129f: C2H3 + H + M9 -> C2H4 + M9 { A = 1.40E+30 n = -3.86 E = 13.89 Ai= 6.08E+12 ni= 0.27 Ei= 1.17 fcA = 0.218 fctA = 207.5 fcb = 0.782 fctb = 2663 fcc = 1.0 fctc = 6095 } G130f: C2H3 + H -> C2H2 + H2 { A = 3.00E+13 n = .00 E = .00 } # Harding, Klippenstein & Georgievskii 2005 G131f: C2H3 + O -> CH2CHO { A = 1.03E+13 n = 0.21 E = -1.79 } G132f: C2H3 + OH -> C2H2 + H2O { A = 5.00E+12 n = .00 E = .00 } G133f: C2H3 + O2 -> C2H2 + HO2 { A = 1.34E+06 n = 1.61 E = -1.61 } G134f: C2H3 + O2 -> CH2CHO + O { A = 3.03E+11 n = 0.29 E = 0.05 } G135f: C2H3 + O2 -> HCO + CH2O { A = 4.58E+16 n = -1.39 E = 4.25 } # Reactions of CH2CHO # Senosiain, Klippenstein & Miller 2006 G136f: CH2CHO -> CH2CO + H { A = 1.32E+34 n = -6.57 E = 206.93 } G137f: CH2CHO -> CH3 + CO { A = 6.51E+34 n = -6.87 E = 197.46 } # Same as for C2H5 + O G138f: CH2CHO + O -> CH2O + HCO { A = 3.17E+13 n = 0.03 E = -1.65 } G139 : CH2CHO + O2 -> OH + CO + CH2O { A = 1.81E+10 n = .00 E = 0.00 } G140 : CH2CHO + O2 -> OH + 2 HCO { A = 2.35E+10 n = .00 E = 0.00 } G141f: CH2CHO + H -> CH3 + HCO { A = 2.20E+13 n = .00 E = 0.00 } G142f: CH2CHO + H -> CH2CO + H2 { A = 1.10E+13 n = .00 E = 0.00 } G143f: CH2CHO + OH -> H2O + CH2CO { A = 1.20E+13 n = .00 E = 0.00 } G144f: CH2CHO + OH -> HCO + CH2OH { A = 3.01E+13 n = .00 E = 0.00 } # Reactions of CH3CHO # Baulch et al. 2005 - HPL - Backward # Modified for collision limit G145f: CH3 + HCO -> CH3CHO { A = 5.00E+13 n = .00 E = .00 } G146f: CH3CHO + O -> CH2CHO + OH { A = 2.92E+12 n = .00 E = 7.57 } G147f: CH3CHO + H -> CH2CHO + H2 { A = 2.05E+09 n = 1.16 E = 10.06 } G148 : CH3CHO + H -> CH3 + CO + H2 { A = 2.05E+09 n = 1.16 E = 10.06 } G149 : CH3CHO + O -> CH3 + CO + OH { A = 2.92E+12 n = .00 E = 7.57 } G150 : CH3CHO + O2 -> CH3 + CO + HO2 { A = 3.01E+13 n = .00 E = 163.80 } G151 : CH3CHO + OH -> CH3 + CO + H2O { A = 2.34E+10 n = .73 E = -4.66 } G152 : CH3CHO + HO2 -> CH3 + CO + H2O2 { A = 3.01E+12 n = .00 E = 49.89 } G153 : CH3CHO + CH3 -> CH3 + CO + CH4 { A = 2.72E+06 n = 1.77 E = 24.77 } # Reactions of C2H4 # Pilla, Davidson, Hanson 2010 G154 : C2H4 + M9 -> H2C2 + H2 + M9 { A = 5.50E+14 n = .00 E = 226.97 } # Miller & Klippenstein 2004 G155f: C2H4 + H + M9 -> C2H5 + M9 { A = 2.03E+39 n = -6.64 E = 24.14 Ai= 1.37E+09 ni= 1.46 Ei= 5.67 fcA = 1.569 fctA = 299 fcb =-0.569 fctb =-9147 fcc = 1.0 fctc = 152.4 } # Huynh, Panasewicz, Ratkiewicz, Truong 2007 # Closer to the recommendation of Baulch et al. 2005 G156f: C2H4 + H -> C2H3 + H2 { A = 1.27E+05 n = 2.75 E = 48.74 } # Nguyen, Vereecken, Hou, Nguyen, Peeters 2005 G157f: C2H4 + O -> CH2CHO + H { A = 7.66E+09 n = 0.88 E = 4.77 } G158f: C2H4 + O -> T-CH2 + CH2O { A = 7.15E+04 n = 2.47 E = 3.89 } G159f: C2H4 + O -> CH3 + HCO { A = 3.89E+08 n = 1.36 E = 3.71 } # Vasu, Hong, Davidson, Hanson, Golden 2010 G160f: C2H4 + OH -> C2H3 + H2O { A = 2.23E+04 n = 2.75 E = 9.27 } # Senosiain, Klippenstein & Miller 2006 G161f: C2H4 + OH -> C2H5O { A = 3.75E+36 n = -7.80 E = 29.54 } G162f: C2H4 + CH3 -> C2H3 + CH4 { A = 2.27E+05 n = 2.00 E = 38.49 } G163f: C2H4 + CH3 + M9 -> N-C3H7 + M9 { A = 3.00E+63 n = -14.6 E = 76.02 Ai= 2.55E+06 ni= 1.60 Ei= 23.85 fcA = 0.8106 fctA = 277 fcb = 0.1894 fctb = 8748 fcc = 1.0 fctc = 7891 } # Reactions of C2H5 G164f: C2H5 + H + M9 -> C2H6 + M9 { A = 1.99E+41 n = -7.08 E = 27.97 Ai= 5.21E+17 ni= -0.99 Ei= 6.61 fcA = 0.1578 fctA = 125 fcb = 0.8422 fctb = 2219 fcc = 1.0 fctc = 6882 } G165f: C2H5 + H -> C2H4 + H2 { A = 2.00E+12 n = .00 E = .00 } # Zhu, Xu & Lin 2004 G166f: C2H5 + CH3 -> C2H4 + CH4 { A = 1.18E+04 n = 2.45 E = 12.22 } # Harding, Klippenstein & Georgievskii 2005 G167f: C2H5 + O -> C2H5O { A = 3.17E+13 n = 0.03 E = -1.65 } # Curran 2006 G168f: C2H5O -> CH3 + CH2O { A = 1.32E+20 n = -2.02 E = 86.82 } G169f: C2H5O -> CH3CHO + H { A = 5.45E+15 n = -0.69 E = 93.01 } # Baulch et al. 2005 G170f: C2H5O + O2 -> CH3CHO + HO2 { A = 2.29E+10 n = .00 E = 3.66 } # Miller, Klippenstein & Robertson 2000 G171f: C2H5 + O2 -> C2H4 + HO2 { A = 1.92E+07 n = 1.02 E = -8.51 } # Oehlschlaeger et al. 2005 G172f: C3H8 + M9 -> C2H5 + CH3 + M9 { A = 5.64E+74 n =-15.74 E = 413.04 Ai= 1.29E+37 ni= -5.84 Ei= 407.47 fcA = 0.69 fctA = 50 fcb = 0.31 fctb = 3000 fcc = 1.0 fctc = 9000 } # Reactions of C2H6 # Oehlschlaeger et al. 2005 G173f: C2H6 + M9 -> 2 CH3 + M9 { A = 3.72E+65 n =-13.14 E = 425.01 Ai= 1.88E+50 ni= -9.72 Ei= 449.12 fcA = 0.61 fctA = 100 fcb = 0.39 fctb = 1900 fcc = 1.0 fctc = 6000 } # Chakraborty, Zhao, Lin, & Truhlar 2006 # Fit 500-2000K G174f: C2H6 + H -> C2H5 + H2 { A = 1.70E+05 n = 2.70 E = 24.02 } # Huynh, Zhang, Truong 2008 G175f: C2H6 + O -> C2H5 + OH { A = 3.17E+01 n = 3.80 E = 13.10 } # Krasnoperov & Michael 2004 G176f: C2H6 + OH -> C2H5 + H2O { A = 1.61E+06 n = 2.22 E = 3.10 } G177f: C2H6 + S-CH2 -> C2H5 + CH3 { A = 4.00E+13 n = .00 E = -2.30 } # Baulch et al. 2005 G178f: C2H6 + CH3 -> C2H5 + CH4 { A = 8.43E+14 n = .00 E = 93.12 } # Reactions of N-C3H7/I-C3H7 # From Tsang 1988 G179f: N-C3H7 + H + M9 -> C3H8 + M9 { A = 4.42E+61 n =-13.55 E = 47.52 Ai= 3.61E+13 ni= .00 Ei= .00 fcA = 0.685 fctA = 369 fcb = 0.315 fctb = 3285 fcc = 1.0 fctc = 6667 } G180f: I-C3H7 + H + M9 -> C3H8 + M9 { A = 1.70E+58 n =-12.08 E = 47.13 Ai= 2.40E+13 ni= .00 Ei= .00 fcA = 0.502 fctA = 1314 fcb = 0.498 fctb = 1314 fcc = 1.0 fctc = 50000 } G181f: N-C3H7 + H -> C2H5 + CH3 { A = 3.70E+24 n = -2.92 E = 52.32 } G182f: I-C3H7 + H -> C2H5 + CH3 { A = 1.40E+28 n = -3.94 E = 66.59 } G183f: N-C3H7 + H -> C3H6 + H2 { A = 1.80E+12 n = .00 E = .00 } G184f: I-C3H7 + H -> C3H6 + H2 { A = 3.20E+12 n = .00 E = .00 } G185f: N-C3H7 + O -> C2H5 + CH2O { A = 9.60E+13 n = .00 E = .00 } G186f: I-C3H7 + O -> CH3CHO + CH3 { A = 9.60E+13 n = .00 E = .00 } G187f: N-C3H7 + OH -> C3H6 + H2O { A = 2.41E+13 n = .00 E = .00 } G188f: I-C3H7 + OH -> C3H6 + H2O { A = 2.41E+13 n = .00 E = .00 } # DeSain, Miller, Klippenstein & Taatjes 2003 G189f: N-C3H7 + O2 -> C3H6 + HO2 { A = 3.70E+16 n = -1.63 E = 14.30 } G190f: I-C3H7 + O2 -> C3H6 + HO2 { A = 6.70E+20 n = -3.02 E = 10.48 } # Knyazev & Slagle 2001 - Total rate # Shafir, Slagle & Knyazev 2003 - Branching ratio G193f: N-C3H7 + CH3 -> C3H6 + CH4 { A = 3.31E+12 n = .00 E = -3.22 } # Curran 2006 - HPL G195f: C3H6 + H + M9 -> N-C3H7 + M9 { A = 6.26E+38 n = -6.66 E = 29.29 Ai= 2.50E+11 ni= 0.51 Ei= 10.96 fcA = 0.0 fctA = 1000 fcb = 1.0 fctb = 1310 fcc = 1.0 fctc = 48097 } G196f: C3H6 + H + M9 -> I-C3H7 + M9 { A = 8.70E+42 n = -7.50 E = 19.75 Ai= 4.24E+11 ni= 0.51 Ei= 5.15 fcA = 0.0 fctA = 1000 fcb = 1.0 fctb = 645.4 fcc = 1.0 fctc = 6844.3 } # Reactions of C3H8 # Carstensen & Dean 2009 G201f: C3H8 + H -> N-C3H7 + H2 { A = 9.36E+07 n = 1.97 E = 34.31 } G202f: C3H8 + H -> I-C3H7 + H2 { A = 7.60E+07 n = 1.86 E = 23.43 } G203f: C3H8 + O -> N-C3H7 + OH { A = 1.90E+05 n = 2.68 E = 15.55 } G204f: C3H8 + O -> I-C3H7 + OH { A = 4.76E+04 n = 2.71 E = 08.81 } # Sivaramkrishnan, Srinivasan, Su, Michael 2009 G205f: C3H8 + OH -> N-C3H7 + H2O { A = 5.15E+03 n = 2.94 E = -1.75 } G206f: C3H8 + OH -> I-C3H7 + H2O { A = 1.81E+05 n = 2.44 E = -2.24 } G207f: C3H8 + CH3 -> N-C3H7 + CH4 { A = 9.03E-01 n = 3.65 E = 29.93 } G208f: C3H8 + CH3 -> I-C3H7 + CH4 { A = 1.51E+00 n = 3.46 E = 29.93 } G209f: C3H8 + HO2 -> N-C3H7 + H2O2 { A = 4.76E+04 n = 2.55 E = 69.00 } G210f: C3H8 + HO2 -> I-C3H7 + H2O2 { A = 9.63E+03 n = 2.60 E = 58.20 } #=========================================================================# # # # C1, C2, and C3 chemistry taken from # # # # "Experimental and Modeling Study of Shock-Tube Oxidation of Acetylene" # # B. Eiteneer and M. Frenklach # # Int. J. Chem. Kinet. 35, 391:414 (2003) # # # #=========================================================================# # Reactions of C2H2 # Laskin & Wang 1999 R001f: C2H2 + M9 -> H2C2 + M9 { A = 2.45E+15 n = -0.64 E = 207.94 } R002f: H2C2 + O2 -> T-CH2 + CO2 { A = 3.30E+12 n = .00 E = .00 } R003f: H2C2 + O2 -> 2 HCO { A = 1.00E+13 n = .00 E = .00 } # Yu & Muckerman 2005 # Rate at T=1000K R004f: C2H2 + S-CH2 -> C3H3 + H { A = 1.90E+14 n = .00 E = .00 } # Miller, Senosiain, Klippenstein, Georgievskii 2008 # Refitted 800K-2500K # Almost pressure indep => Rate 1bar R005f: P-C3H4 + H -> C2H2 + CH3 { A = 3.46E+12 n = 0.44 E = 22.86 } R006f: A-C3H4 + H -> C2H2 + CH3 { A = 8.95E+13 n = -0.02 E = 47.07 } # P=1bar R007f: C2H2 + CH3 -> S-C3H5 { A = 7.45E+43 n =-10.13 E = 77.50 } # P=10bar #007f: C2H2 + CH3 -> S-C3H5 { A = 2.23E+43 n = -9.62 E = 84.46 } # Ceursters, Nguyen, Peeters, Nguyen 2000 R008f: C2H2 + C2H -> N-C4H3 { A = 7.80E+13 n = .00 E = .00 } R009f: C2H2 + HCCO -> C3H3 + CO { A = 1.00E+11 n = .00 E = 12.55 } # Reactions of C2H3 R010f: C2H3 + H2O2 -> C2H4 + HO2 { A = 1.21E+10 n = .00 E = -2.49 } R011f: C2H3 + HCO -> C2H4 + CO { A = 9.00E+13 n = .00 E = .00 } R012f: C2H3 + HCO -> C2H3CHO { A = 1.80E+13 n = .00 E = .00 } # Stoliarov et al. 2002 # Indep of pressure R013f: C2H3 + CH3 -> C2H2 + CH4 { A = 9.03E+12 n = .00 E = -3.20 } # Rates fitted at 1.33 bar - 500K to 2400K R014f: C3H6 -> C2H3 + CH3 { A = 4.04E+42 n = -7.67 E = 467.90 } R015f: C2H3 + CH3 -> A-C3H5 + H { A = 1.93E+18 n = -1.25 E = 32.09 } # Harding, Klippenstein, & Georgievskii 2007 # -> High pressure limit # Stoliarov et al. 2002 # -> Fall-off at 1.33bar - 900K to 3000K R016f: A-C3H5 + H -> C3H6 { A = 5.93E+54 n =-11.76 E = 98.53 } # Reaction of C2H R017f: C2H + CH3 -> C3H3 + H { A = 2.41E+13 n = .00 E = .00 } # Reactions of C2O R018f: C2O + H -> CH + CO { A = 5.00E+13 n = .00 E = .00 } R019f: C2O + O -> CO + CO { A = 5.00E+13 n = .00 E = .00 } R020f: C2O + OH -> H + CO + CO { A = 2.00E+13 n = .00 E = .00 } R021f: C2O + O2 -> O + CO + CO { A = 2.00E+13 n = .00 E = .00 } # Reactions of HCCO R022f: HCCO + CH3 -> C2H4 + CO { A = 5.00E+13 n = .00 E = .00 } R023f: HCCO + OH -> C2O + H2O { A = 3.00E+13 n = .00 E = .00 } R024f: HCCO + OH -> 2 HCO { A = 1.00E+13 n = .00 E = .00 } # Reactions of CH2CO R025f: CH2CO + OH -> CH2OH + CO { A = 5.00E+12 n = .00 E = .00 } R026f: CH2CO + T-CH2 -> C2H4 + CO { A = 1.00E+12 n = .00 E = .00 } R027f: CH2CO + T-CH2 -> HCCO + CH3 { A = 3.60E+13 n = .00 E = 46.02 } # Woods & Haynes 1994 R028f: CH2CO + CH3 -> C2H5 + CO { A = 9.00E+10 n = .00 E = .00 } R029f: CH2CO + CH3 -> HCCO + CH4 { A = 7.50E+12 n = .00 E = 54.39 } # Reactions of CH2CHO R030f: CH2CHO + CH3 -> C2H5 + HCO { A = 4.90E+14 n = -0.50 E = .00 } # Reactions of C2H4 R031f: C2H4 + C2H -> C4H4 + H { A = 1.20E+13 n = .00 E = .00 } R032f: C2H4 + O2 -> C2H3 + HO2 { A = 4.22E+13 n = .00 E = 259.83 } # Wang 2001 R033 : C2H4 + O2 -> CH3 + CO2 + H { A = 4.90E+12 n = 0.42 E = 317.15 } # Reactions of C2H5 R034f: C2H5 + HCO -> C2H6 + CO { A = 1.20E+14 n = .00 E = .00 } R035f: C2H5 + HO2 -> C2H6 + O2 { A = 3.00E+11 n = .00 E = .00 } R036f: C2H5 + HO2 -> C2H4 + H2O2 { A = 3.00E+11 n = .00 E = .00 } # Ludwig et al. .2006 R037f: C2H5 + HO2 -> C2H5O + OH { A = 3.10E+13 n = .00 E = .00 } # Carstensen & Dean 2005 R038f: C2H6 + HO2 -> C2H5 + H2O2 { A = 2.61E+02 n = 3.37 E = 66.58 } # Reactions of C3H2 R039f: C3H2 + O -> C3H2O { A = 1.36E+14 n = .00 E = .00 } R040f: C3H2 + OH -> C2H2 + HCO { A = 1.00E+13 n = .00 E = .00 } R041f: C3H2 + O2 -> HCCO + CO + H { A = 1.25E+11 n = .00 E = 4.18 } R042f: C3H2 + CH -> C4H2 + H { A = 5.00E+13 n = .00 E = .00 } R043f: C3H2 + T-CH2 -> N-C4H3 + H { A = 5.00E+13 n = .00 E = .00 } R044f: C3H2 + CH3 -> C4H4 + H { A = 5.00E+12 n = .00 E = .00 } R045f: C3H2 + HCCO -> N-C4H3 + CO { A = 1.00E+13 n = .00 E = .00 } # Reactions of C3H2O # Estimated R046f: C2H + HCO -> C3H2O { A = 5.00E+13 n = .00 E = .00 } # From P-C3H4 + H R200f: C3H2O + H -> C2H2 + HCO { A = 3.46E+12 n = 0.44 E = 22.86 } # Taken from CH3CHO R047 : C3H2O + H -> C2H + CO + H2 { A = 2.05E+09 n = 1.16 E = 10.06 } R048 : C3H2O + O -> C2H + CO + OH { A = 2.92E+12 n = .00 E = 7.57 } R049 : C3H2O + O2 -> C2H + CO + HO2 { A = 3.01E+13 n = .00 E = 163.80 } R050 : C3H2O + OH -> C2H + CO + H2O { A = 2.34E+10 n = .73 E = -4.66 } R051 : C3H2O + HO2 -> C2H + CO + H2O2 { A = 3.01E+12 n = .00 E = 49.89 } R052 : C3H2O + CH3 -> C2H + CO + CH4 { A = 2.72E+06 n = 1.77 E = 24.77 } # Reactions of C3H3 # 2x rate for C2H3+H R053f: C3H2 + H + M9 -> C3H3 + M9 { A = 2.80E+30 n = -3.86 E = 13.89 Ai= 1.02E+13 ni= .27 Ei= 1.17 fcA = 0.218 fctA = 207.5 fcb = 0.782 fctb = 2663 fcc = 1.0 fctc = 6095 } # Miller & Klippenstein 2003 (1bar) # P=1bar R054f: C3H3 + H -> C3H2 + H2 { A = 1.10E+10 n = 1.13 E = 58.28 } R055f: C3H3 + H -> P-C3H4 { A = 7.94E+29 n = -5.06 E = 20.34 } R056f: C3H3 + H -> A-C3H4 { A = 3.16E+29 n = -5.00 E = 19.71 } # P=10bar #054f: C3H3 + H -> C3H2 + H2 { A = 3.31E+13 n = 0.20 E = 73.55 } #055f: C3H3 + H -> P-C3H4 { A = 1.07E+24 n = -3.15 E = 13.64 } #056f: C3H3 + H -> A-C3H4 { A = 8.71E+23 n = -3.20 E = 13.62 } # Adapted from C2H2 + OH R057f: C3H3 + OH -> C2H3CHO { A = 7.53E+06 n = 1.55 E = 8.81 } R058f: C3H3 + OH -> C2H4 + CO { A = 1.28E+09 n = 0.73 E = 10.79 } # 1/2 rate for C2H4+OH R059f: C3H3 + OH -> C3H2 + H2O { A = 1.13E+05 n = 2.28 E = 10.32 } R060f: C3H3 + OH -> CH2O + C2H2 { A = 1.88E+36 n = -7.80 E = 29.54 } # Lee, Nam & Choi 2006 # Kwon, Nam, Youn, Joo, Lee, & Choi 2006 # Slagle, Gmurczyk, Batt & Gutman 1991 R061f: C3H3 + O -> C3H2O + H { A = 1.38E+14 n = .00 E = .00 } # Hahn, Klippenstein, Miller 2001 R062f: C3H3 + O2 -> CH2CO + HCO { A = 1.70E+05 n = 1.70 E = 6.28 } R063 : C3H3 + HO2 -> OH + CO + C2H3 { A = 8.00E+11 n = .00 E = .00 } # Wang 2001 R064f: C3H3 + HO2 -> A-C3H4 + O2 { A = 3.00E+11 n = .00 E = .00 } R065f: C3H3 + HO2 -> P-C3H4 + O2 { A = 3.00E+11 n = .00 E = .00 } R066f: P-C3H4 + O2 -> CH3 + HCO + CO { A = 4.00E+14 n = .00 E = 175.43 } R067f: C3H3 + HCO -> A-C3H4 + CO { A = 2.50E+13 n = .00 E = .00 } R068f: C3H3 + HCO -> P-C3H4 + CO { A = 2.50E+13 n = .00 E = .00 } R069f: C3H3 + CH -> I-C4H3 + H { A = 5.00E+13 n = .00 E = .00 } # Miller, Melius 1992 R070f: C3H3 + T-CH2 -> C4H4 + H { A = 5.00E+13 n = .00 E = .00 } # Reactions of C3H4 # Miller & Klippenstein 2003 (1bar) # P=1bar R071f: A-C3H4 -> P-C3H4 { A = 7.76E+39 n = -7.80 E = 328.22 } # P=10bar #071f: A-C3H4 -> P-C3H4 { A = 4.79E+48 n =-10.00 E = 371.06 } # Miller, Senosiain, Klippenstein, Georgievskii 2008 # Refitted 800K-2500K # Almost pressure indep => Rate 1bar R073f: A-C3H4 + H -> P-C3H4 + H { A = 2.47E+15 n = -0.33 E = 26.93 } # P=1bar R074f: A-C3H4 + H -> A-C3H5 { A = 2.01E+49 n =-10.77 E = 82.10 } R075f: A-C3H4 + H -> T-C3H5 { A = 6.70E+42 n =-12.46 E = 68.45 } R076f: P-C3H4 + H -> T-C3H5 { A = 8.83E+52 n =-12.36 E = 68.81 } R077f: P-C3H4 + H -> S-C3H5 { A = 1.53E+49 n =-11.97 E = 59.18 } # P=10bar #074f: A-C3H4 + H -> A-C3H5 { A = 2.59E+45 n = -9.37 E = 83.83 } #075f: A-C3H4 + H -> T-C3H5 { A = 1.24E+51 n =-11.59 E = 73.98 } #076f: P-C3H4 + H -> T-C3H5 { A = 1.04E+51 n =-11.46 E = 73.95 } #077f: P-C3H4 + H -> S-C3H5 { A = 1.92E+50 n =-11.81 E = 69.83 } # 1/2 the rate for C2H6 R078f: P-C3H4 + H -> C3H3 + H2 { A = 8.50E+04 n = 2.70 E = 24.02 } R079f: P-C3H4 + O -> C3H3 + OH { A = 4.49E+07 n = 1.92 E = 23.81 } R080f: P-C3H4 + OH -> C3H3 + H2O { A = 8.05E+05 n = 2.22 E = 3.10 } R081f: P-C3H4 + CH3 -> C3H3 + CH4 { A = 4.22E+14 n = .00 E = 93.12 } R082f: P-C3H4 + HO2 -> C3H3 + H2O2 { A = 1.30E+02 n = 3.37 E = 66.58 } # Same as for C2H4 R083f: A-C3H4 + H -> C3H3 + H2 { A = 1.33E+06 n = 2.53 E = 51.21 } R084f: A-C3H4 + OH -> C3H3 + H2O { A = 1.31E-01 n = 4.20 E = -3.60 } R085f: A-C3H4 + CH3 -> C3H3 + CH4 { A = 2.27E+05 n = 2.00 E = 38.49 } R086f: A-C3H4 + HO2 -> C3H3 + H2O2 { A = 9.76E+10 n = 0.12 E = 97.78 } # Nguyen, Peeters & Vereecken 2006 # Total rate assigned R087f: A-C3H4 + O -> CH2CO + T-CH2 { A = 9.63E+06 n = 2.05 E = 0.75 } # Adapted from C2H2+O # 1/2 of the rate R088f: P-C3H4 + O -> HCCO + CH3 { A = 4.05E+06 n = 2.00 E = 7.95 } R089f: P-C3H4 + O -> C2H4 + CO { A = 6.25E+06 n = 2.00 E = 7.95 } R090f: A-C3H4 + C2H -> C2H2 + C3H3 { A = 1.00E+13 n = .00 E = .00 } R091f: P-C3H4 + C2H -> C2H2 + C3H3 { A = 1.00E+13 n = .00 E = .00 } # From C2H2 + OH R092f: P-C3H4 + OH -> HCCOH + CH3 { A = 2.41E+06 n = 2.00 E = 53.19 } R093f: P-C3H4 + OH -> CH2CO + CH3 { A = 7.53E+06 n = 1.55 E = 8.81 } R094f: P-C3H4 + OH -> C2H5 + CO { A = 1.28E+09 n = 0.73 E = 10.79 } # Reactions of C2H3CHO # Baulch et al. 2005 - adapted from CH3CHO R095 : C2H3CHO + H -> C2H3 + CO + H2 { A = 4.09E+09 n = 1.16 E = 10.06 } R096 : C2H3CHO + O -> C2H3 + CO + OH { A = 5.84E+12 n = .00 E = 7.57 } R097 : C2H3CHO + OH -> C2H3 + CO + H2O { A = 2.89E+08 n = 1.35 E = -6.58 } R098 : C2H3CHO + HO2 -> C2H3 + CO + H2O2 { A = 4.09E+04 n = 2.50 E = 42.69 } R099 : C2H3CHO + CH3 -> C2H3 + CO + CH4 { A = 3.49E-08 n = 6.21 E = 6.82 } # Reactions of C3H5 # Davis, Law, Wang 1999 (1bar) R100f: A-C3H5 -> T-C3H5 { A = 7.06E+56 n =-14.08 E = 317.43 } R101f: A-C3H5 -> S-C3H5 { A = 5.00E+51 n =-13.02 E = 306.69 } R102f: T-C3H5 -> S-C3H5 { A = 1.50E+48 n =-12.71 E = 225.52 } # Klippenstein, Harding, Georgievskii, Miller 2008 # Fitted 400K-2500K R103f: A-C3H5 + H -> A-C3H4 + H2 { A = 9.56E+03 n = 2.80 E = 13.77 } # Tsang 1991 R104f: A-C3H5 + OH -> A-C3H4 + H2O { A = 6.03E+12 n = .00 E = .00 } R105f: A-C3H5 + CH3 -> A-C3H4 + CH4 { A = 3.01E+12 n = -0.32 E = -0.55 } R106f: A-C3H5 + C2H3 -> A-C3H4 + C2H4 { A = 2.41E+12 n = .00 E = .00 } R107f: A-C3H5 + C2H5 -> A-C3H4 + C2H6 { A = 9.64E+11 n = .00 E = -0.55 } # NC7 mechanism from LLNL R108f: A-C3H5 + A-C3H5 -> A-C3H4 + C3H6 { A = 1.00E+12 n = .00 E = .00 } # Lee & Bozzelli 2005 R109f: A-C3H5 + O2 -> A-C3H4 + HO2 { A = 2.06E+04 n = 2.19 E = 73.60 } R110f: A-C3H5 + O2 -> C2H3CHO + OH { A = 3.36E+05 n = 1.81 E = 80.29 } R111 : A-C3H5 + O2 -> C2H2 + CH2O + OH { A = 9.71E+20 n = -2.70 E = 104.52 } R112f: A-C3H5 + O2 -> CH2CHO + CH2O { A = 3.08E+09 n = 0.37 E = 70.75 } # From C2H5+O # Estimated from collision limit R113f: A-C3H5 + O -> C3H5O { A = 2.00E+14 n = .00 E = .00 } R114f: A-C3H5 + OH -> C2H3CHO + H2 { A = 4.20E+32 n = -5.16 E = 126.05 } R115f: A-C3H5 + HCO -> C3H6 + CO { A = 6.00E+13 n = .00 E = .00 } R116f: A-C3H5 + HO2 -> C3H6 + O2 { A = 2.66E+12 n = .00 E = .00 } # From A1CH2+HO2 R117f: A-C3H5 + HO2 -> C3H5O + OH { A = 1.19E+09 n = 1.03 E = -9.41 } # Reactions of T-C3H5 R119f: T-C3H5 + H -> P-C3H4 + H2 { A = 3.34E+12 n = .00 E = .00 } R120f: T-C3H5 + O -> CH3 + CH2CO { A = 6.00E+13 n = .00 E = .00 } R121 : T-C3H5 + OH -> CH3 + CH2CO + H { A = 5.00E+12 n = .00 E = .00 } R122 : T-C3H5 + HO2 -> CH3 + CH2CO + OH { A = 2.00E+13 n = .00 E = .00 } R123f: T-C3H5 + HCO -> C3H6 + CO { A = 9.00E+13 n = .00 E = .00 } R124f: T-C3H5 + CH3 -> P-C3H4 + CH4 { A = 1.00E+11 n = .00 E = .00 } # Reactions of S-C3H5 R125f: S-C3H5 + H -> P-C3H4 + H2 { A = 3.34E+12 n = .00 E = .00 } R126f: S-C3H5 + O -> C2H4 + HCO { A = 6.00E+13 n = .00 E = .00 } R127 : S-C3H5 + OH -> C2H4 + HCO + H { A = 5.00E+12 n = .00 E = .00 } R128 : S-C3H5 + HO2 -> C2H4 + HCO + OH { A = 2.00E+13 n = .00 E = .00 } R129f: S-C3H5 + HCO -> C3H6 + CO { A = 9.00E+13 n = .00 E = .00 } R130f: S-C3H5 + CH3 -> P-C3H4 + CH4 { A = 1.00E+11 n = .00 E = .00 } # Adapted from C2H5/C2H3+O2 R131f: T-C3H5 + O2 -> A-C3H4 + HO2 { A = 1.92E+07 n = 1.02 E = -8.51 } R132f: S-C3H5 + O2 -> P-C3H4 + HO2 { A = 1.34E+06 n = 1.61 E = -1.61 } R133 : T-C3H5 + O2 -> CH3 + CO + CH2O { A = 4.58E+16 n = -1.39 E = 4.25 } R134f: S-C3H5 + O2 -> CH3CHO + HCO { A = 4.58E+16 n = -1.39 E = 4.25 } # Reactions of C3H5O # NC7 path from LLNL R135f: C3H5O + O2 -> C2H3CHO + HO2 { A = 1.00E+12 n = .00 E = 25.10 } R136f: C3H5O -> C2H3CHO + H { A = 1.00E+14 n = .00 E = 121.75 } R137f: C3H5O -> C2H3 + CH2O { A = 2.03E+12 n = 0.09 E = 98.58 } # Reactions of C3H6 R138f: C3H6 + H -> C2H4 + CH3 { A = 8.00E+21 n = -2.39 E = 46.78 } # Adapted from C2H4 R139f: C3H6 + O -> CH2CHO + CH3 { A = 5.09E+07 n = 1.66 E = 2.75 } R140f: C3H6 + O -> C2H5 + HCO { A = 1.95E+08 n = 1.36 E = 3.71 } R141f: C3H6 + O -> C2H3CHO + 2H { A = 3.83E+09 n = 0.88 E = 4.77 } # Carstensen & Dean 2009 R142f: C3H6 + H -> A-C3H5 + H2 { A = 2.03E+06 n = 2.28 E = 19.75 } # Rate from C3H8 + X (x0.5) R143f: C3H6 + O -> A-C3H5 + OH { A = 9.95E+04 n = 2.68 E = 15.55 } R144f: C3H6 + HO2 -> A-C3H5 + H2O2 { A = 2.38E+04 n = 2.55 E = 69.00 } R145f: C3H6 + CH3 -> A-C3H5 + CH4 { A = 4.57E-01 n = 3.65 E = 29.93 } # From C2H4 (x0.25) R146f: C3H6 + H -> T-C3H5 + H2 { A = 3.18E+04 n = 2.75 E = 48.74 } R147f: C3H6 + CH3 -> T-C3H5 + CH4 { A = 5.68E+05 n = 2.00 E = 38.49 } # From C2H4 (x0.5) R148f: C3H6 + H -> S-C3H5 + H2 { A = 6.35E+04 n = 2.75 E = 48.74 } R149f: C3H6 + CH3 -> S-C3H5 + CH4 { A = 1.14E+05 n = 2.00 E = 38.49 } # Zador, Jasper, Miller 2009 # Vasu, Hong, Davidson, Hanson 2010 R150f: C3H6 + OH -> A-C3H5 + H2O { A = 1.89E+05 n = 2.50 E = 2.80 } R151f: C3H6 + OH -> T-C3H5 + H2O { A = 4.67E+04 n = 2.47 E = 7.31 } R152f: C3H6 + OH -> S-C3H5 + H2O { A = 5.07E+03 n = 2.85 E = 8.85 } #==========================================================================# # # # Diacetylene Chemistry # # # # "Shock-Tube and Modeling Study of Diacetylene Pyrolysis and Oxidation" # # Y. Hidaka, Y. Henmi, T. Ohonishi & T. Okuno # # Combustion and Flame 130:62-82 (2002) # # # #==========================================================================# # Reactions of C4H # From C2H H01f: C4H + O2 -> C2H + 2CO { A = 1.00E+13 n = .00 E = -3.16 } # Reactions of C4H2 # Adapted from C2H2 H02f: C4H + H -> C4H2 { A = 6.00E+13 n = .00 E = .00 } H03f: C4H2 + H -> C4H + H2 { A = 3.20E+09 n = 1.80 E = 125.97 } H04f: C4H2 + H2 -> C4H4 { A = 4.00E+14 n = .00 E = 225.52 } H05 : C4H2 + C4H2 -> C8H2 + H + H { A = 1.51E+14 n = .00 E = 234.30 } H06f: C4H2 + C4H2 -> C8H2 + H2 { A = 1.51E+13 n = .00 E = 178.66 } H07f: C4H2 + O2 -> HCCO + HCCO { A = 9.56E+12 n = .00 E = 130.12 } # From C2H2 - Recombined H08f: C4H2 + O -> C3H2 + CO { A = 2.06E+07 n = 2.00 E = 7.95 } # Klippenstein & Miller 2005 # Refitted H09f: C4H2 + H + M9 -> I-C4H3 + M9 { Ai= 4.31E+10 ni= 1.16 Ei= 7.33 A = 2.30E+45 n = -8.10 E = 10.49 fcA = 0.0748 fctA = -4216 fcB = 0.0 fctB = 1 fcc = 0.0 fctc = 1 } H10f: C4H2 + H -> N-C4H3 { A = 1.37E+39 n = -7.87 E = 64.61 } # Senosiain, Klippenstein & Miller 2007 # Lumping: C4H2O+H = C3H3+CO H11f: C4H2 + OH -> C4H + H2O { A = 9.15E+09 n = 1.03 E = 90.99 } H12f: C4H2 + OH -> C3H3 + CO { A = 3.30E+12 n = -0.25 E = 9.94 } # Reactions of C4H3 # Wang & Frenklach 1994 ?? H13f: N-C4H3 -> I-C4H3 { A = 4.10E+43 n = -9.50 E = 221.75 } H14f: N-C4H3 + H -> I-C4H3 + H { A = 2.50E+20 n = -1.67 E = 45.19 } H15f: N-C4H3 + H -> C4H4 { A = 2.00E+47 n =-10.26 E = 54.68 } H16f: I-C4H3 + H -> C4H4 { A = 3.40E+43 n = -9.01 E = 50.71 } H17f: N-C4H3 + H -> C2H2 + C2H2 { A = 6.30E+25 n = -3.34 E = 41.88 } H18f: I-C4H3 + H -> C2H2 + C2H2 { A = 2.80E+23 n = -2.55 E = 45.10 } # From C2H3+X H19f: N-C4H3 + H -> C4H2 + H2 { A = 1.50E+13 n = .00 E = .00 } H20f: I-C4H3 + H -> C4H2 + H2 { A = 3.00E+13 n = .00 E = .00 } H21f: N-C4H3 + OH -> C4H2 + H2O { A = 2.50E+12 n = .00 E = .00 } H22f: I-C4H3 + OH -> C4H2 + H2O { A = 5.00E+12 n = .00 E = .00 } H23f: N-C4H3 + O2 -> C4H2 + HO2 { A = 6.70E+05 n = 1.61 E = -1.61 } H24f: I-C4H3 + O2 -> C4H2 + HO2 { A = 1.34E+06 n = 1.61 E = -1.61 } H25f: I-C4H3 + O -> CH2CO + C2H { A = 2.00E+13 n = .00 E = .00 } H26f: I-C4H3 + O2 -> HCCO + CH2CO { A = 1.63E+11 n = .00 E = -7.53 } # From C3H3 + O2 H27f: I-C4H3 + O2 -> HCO + C2H2 + CO { A = 1.70E+05 n = 1.70 E = 6.28 } # Reactions of C4H4 # From C2H4+X H28f: C4H4 + H -> N-C4H3 + H2 { A = 1.27E+05 n = 2.75 E = 48.74 } H29f: C4H4 + H -> I-C4H3 + H2 { A = 6.35E+04 n = 2.75 E = 48.74 } H30f: C4H4 + OH -> N-C4H3 + H2O { A = 6.55E-02 n = 4.20 E = -3.60 } H31f: C4H4 + OH -> I-C4H3 + H2O { A = 3.28E-02 n = 4.20 E = -3.60 } H32f: C4H4 + CH3 -> N-C4H3 + CH4 { A = 1.14E+05 n = 2.00 E = 38.49 } H33f: C4H4 + CH3 -> I-C4H3 + CH4 { A = 5.68E+04 n = 2.00 E = 38.49 } # From C2H2 (x1/2) H34f: C4H4 + O -> A-C3H4 + CO { A = 6.25E+06 n = 2.00 E = 7.95 } # From C2H4 (x1/2) H35f: C4H4 + O -> C3H2 + CH2O { A = 3.58E+04 n = 2.47 E = 3.89 } H36f: C4H4 + O -> C3H3 + HCO { A = 1.95E+08 n = 1.36 E = 3.71 } # Reactions of C6H2 & C8H2 # Ceursters, Nguyen, Peeters, Nguyen 2000 H37f: C4H2 + C2H -> C6H2 + H { A = 7.80E+13 n = .00 E = .00 } H38f: C2H2 + C4H -> C6H2 + H { A = 7.80E+13 n = .00 E = .00 } H39f: C6H2 + C2H -> C8H2 + H { A = 7.80E+13 n = .00 E = .00 } H40f: C4H2 + C4H -> C8H2 + H { A = 7.80E+13 n = .00 E = .00 } #==========================================================================# # # # Butadiene Chemistry # # # # "Detailed kinetic modelling of butadiene Oxidation at high temperatures" # # A. Laskin, H. Wang, C. Law. # # Int. J. Chem. Kinet. 2000. 32-589 # # # #==========================================================================# B00f: H2C2 + C2H4 -> C4H6 { A = 1.00E+12 n = .00 E = .00 } # From C2H2 + CH2 B01f: H2C2 + C2H2 -> C4H4 { A = 1.90E+14 n = .00 E = .00 } # Miller, Klippenstein & Robertson 2000 B02f: C2H3 + C2H2 -> N-C4H5 { A = 1.32E+12 n = 0.16 E = 34.78 } # Bauclh et al. 2005 # Full rate to addition B04f: 2 C2H3 -> C4H6 { A = 8.43E+13 n = .00 E = .00 } # Wang & Frenklach 1997 B05f: 2 C2H3 -> I-C4H5 + H { A = 1.20E+22 n = -2.44 E = 57.13 } B06f: 2 C2H3 -> N-C4H5 + H { A = 2.40E+20 n = -2.04 E = 64.28 } B07f: 2 C2H3 -> C2H2 + C2H4 { A = 9.60E+11 n = .00 E = .00 } B08f: C3H3 + CH3 + M9 -> C4H6 + M9 { A = 2.60E+57 n =-11.94 E = 40.89 Ai= 1.50E+12 ni= .00 Ei= .00 fcA = 0.825 fctA = 1340.6 fcb = 0.175 fctb = 60000 fcc = 1.0 fctc = 9769.8 } B09f: C3H6 + C2H3 -> C4H6 + CH3 { A = 7.23E+11 n = .00 E = 20.92 } # Wang & Frenklach 1997 B10f: C4H6 -> I-C4H5 + H { A = 5.70E+36 n = -6.27 E = 470.09 } B11f: C4H6 -> N-C4H5 + H { A = 5.30E+44 n = -8.62 E = 517.18 } B12f: C4H6 -> C4H4 + H2 { A = 2.50E+15 n = .00 E = 396.22 } # Lumping species 12-C4H6 into C4H6 B14f: P-C3H4 + CH3 -> C4H6 + H { A = 8.94E+07 n = 1.14 E = 51.80 } B15f: A-C3H4 + CH3 -> C4H6 + H { A = 2.83E+08 n = 1.06 E = 46.70 } B16f: C4H6 + H -> N-C4H5 + H2 { A = 1.33E+06 n = 2.53 E = 51.21 } B17f: C4H6 + H -> I-C4H5 + H2 { A = 6.65E+05 n = 2.53 E = 38.66 } # Estimated from backward reaction B18f: N-C4H5 + OH -> C4H6 + O { A = 2.20E+11 n = .00 E = .00 } B19f: C4H6 + O -> I-C4H5 + OH { A = 7.50E+06 n = 1.90 E = 15.65 } B20f: C4H6 + OH -> N-C4H5 + H2O { A = 6.20E+06 n = 2.00 E = 14.35 } B21f: C4H6 + OH -> I-C4H5 + H2O { A = 3.10E+06 n = 2.00 E = 1.80 } B22f: C4H6 + CH3 -> N-C4H5 + CH4 { A = 2.00E+14 n = .00 E = 95.54 } B23f: C4H6 + CH3 -> I-C4H5 + CH4 { A = 1.00E+14 n = .00 E = 82.84 } B24f: C4H6 + C2H3 -> N-C4H5 + C2H4 { A = 5.00E+13 n = .00 E = 95.54 } B25f: C4H6 + C2H3 -> I-C4H5 + C2H4 { A = 2.50E+13 n = .00 E = 82.84 } # From C2H4 + O B28 : C4H6 + O -> A-C3H5 + CO + H { A = 7.66E+09 n = 0.88 E = 4.77 } B29f: C4H6 + O -> P-C3H4 + CH2O { A = 7.15E+04 n = 2.47 E = 3.89 } B30f: C4H6 + O -> A-C3H5 + HCO { A = 3.89E+08 n = 1.36 E = 3.71 } # From C2H4 + OH B31f: C4H6 + OH -> A-C3H5 + CH2O { A = 3.75E+36 n = -7.80 E = 29.54 } # Wang & Frenklach 1994 B32f: C4H4 + H -> N-C4H5 { A = 1.30E+51 n =-11.92 E = 69.04 } B33f: C4H4 + H -> I-C4H5 { A = 4.90E+51 n =-11.92 E = 74.06 } # Wang & Frenklach 1994 B34f: N-C4H5 -> I-C4H5 { A = 1.50E+67 n =-16.89 E = 247.30 } # Wang & Frenklach 1997 B35f: N-C4H5 + H -> I-C4H5 + H { A = 3.10E+26 n = -3.35 E = 72.90 } B36f: N-C4H5 + H -> C4H4 + H2 { A = 1.50E+13 n = .00 E = .00 } B37f: N-C4H5 + OH -> C4H4 + H2O { A = 2.00E+12 n = .00 E = .00 } B38f: N-C4H5 + HCO -> C4H6 + CO { A = 5.00E+12 n = .00 E = .00 } B39f: N-C4H5 + H2O2 -> C4H6 + HO2 { A = 1.21E+10 n = .00 E = -2.49 } B40f: N-C4H5 + HO2 -> C4H6 + O2 { A = 6.00E+11 n = .00 E = .00 } # From C2H3 + O B99f: N-C4H5 + O -> A-C3H5 + CO { A = 1.03E+13 n = 0.21 E = -1.79 } # From C2H3 + O2 B41f: N-C4H5 + O2 -> C4H4 + HO2 { A = 1.34E+06 n = 1.61 E = -1.61 } B42 : N-C4H5 + O2 -> A-C3H5 + CO + O { A = 3.03E+11 n = 0.29 E = 0.05 } B43f: N-C4H5 + O2 -> HCO + C2H3CHO { A = 4.58E+16 n = -1.39 E = 4.25 } B44f: I-C4H5 + H -> C4H4 + H2 { A = 3.00E+13 n = .00 E = .00 } B45f: I-C4H5 + H -> C3H3 + CH3 { A = 2.00E+13 n = .00 E = 8.37 } B46f: I-C4H5 + OH -> C4H4 + H2O { A = 4.00E+12 n = .00 E = .00 } B47f: I-C4H5 + HCO -> C4H6 + CO { A = 5.00E+12 n = .00 E = .00 } B48f: I-C4H5 + HO2 -> C4H6 + O2 { A = 6.00E+11 n = .00 E = .00 } B49f: I-C4H5 + H2O2 -> C4H6 + HO2 { A = 1.21E+10 n = .00 E = -2.49 } B50f: I-C4H5 + O2 -> CH2CO + CH2CHO { A = 2.16E+10 n = .00 E = 10.46 } # From C2H5 + O B51f: I-C4H5 + O -> C3H3 + CH2O { A = 3.17E+13 n = 0.03 E = -1.65 } B52f: N-C4H5 + C2H3 -> A1-C6H6 + H2 { A = 1.84E-13 n = 7.07 E = -15.11 } #==========================================================================# # # # Reduced Heptane mechanism # # Lawrence Livermore n-Heptane Mechanism - ver 2b # # # # "A Comprehensive Modeling Study of n-Heptane Oxidation" # # Curran, H. J., Gaffuri, P., Pitz, W. J., and Westbrook, C. K. # # Combustion and Flame 114:149-177 (1998). # # # # UCRL-WEB-204236 - Review and release date: May 19, 2004. # # # #==========================================================================# # ------------------- HIGH TEMPERATURE -------------------- # # ---------------------- 14 Species ----------------------- # # --------------------- 72 Reactions ---------------------- # # Reactions of N-C7H16 HP00 : N-C7H16 -> C5H11 + C2H5 { A = 8.10E+77 n =-17.62 E = 503.75 } HP01 : N-C7H16 -> P-C4H9 + N-C3H7 { A = 1.42E+78 n =-17.71 E = 505.01 } HP02 : N-C7H16 + H -> C7H15 + H2 { A = 1.75E+06 n = 2.60 E = 18.25 } HP03 : N-C7H16 + O -> C7H15 + OH { A = 1.72E+05 n = 2.81 E = 9.46 } HP04 : N-C7H16 + OH -> C7H15 + H2O { A = 7.40E+08 n = 1.50 E = 1.08 } HP05 : N-C7H16 + O2 -> C7H15 + HO2 { A = 2.89E+13 n = 0.20 E = 209.66 } HP06 : N-C7H16 + HO2 -> C7H15 + H2O2 { A = 7.57E+12 n = 0.21 E = 73.78 } HP07 : C7H15 + H -> N-C7H16 { A = 1.21E+81 n =-19.78 E = 163.27 } HP08 : C7H15 + HO2 -> N-C7H16 + O2 { A = 1.16E+08 n = 0.98 E = -6.40 } # Reactions of C7H15 HP09 : C7H15 -> C5H11 + C2H4 { A = 1.89E+12 n = 0.02 E = 116.25 } HP10 : C7H15 -> P-C4H9 + C3H6 { A = 7.73E+18 n = -1.75 E = 133.78 } HP11 : C7H15 -> N-C3H7 + P-C4H8 { A = 2.53E+18 n = -1.65 E = 132.56 } HP12 : C7H15 -> C2H5 + C5H10 { A = 2.49E+16 n = -1.18 E = 123.50 } HP13 : C7H15 -> C7H14 + H { A = 1.41E+15 n = -0.53 E = 156.52 } HP14 : C7H14 + H -> C7H15 { A = 6.66E+11 n = 0.45 E = 8.43 } HP15 : C7H15 + HO2 -> C7H15O + OH { A = 7.00E+12 n = .00 E = -4.18 } HP16 : C7H15 + CH3O2 -> C7H15O + CH3O { A = 7.00E+12 n = .00 E = -4.18 } # Reactions of C7H15O HP17 : C7H15O -> C3H7CHO + N-C3H7 { A = 6.18E+16 n = -1.36 E = 77.48 } HP18 : C7H15O -> C2H5 + HCO + P-C4H9 { A = 2.23E+15 n = -0.70 E = 77.85 } HP19 : C7H15O -> CH3CHO + C5H11 { A = 8.92E+19 n = -2.03 E = 87.88 } # Reactions of C7H14 HP20 : C7H14 -> C4H7 + N-C3H7 { A = 1.19E+22 n = -1.87 E = 308.01 } HP21 : C7H14 -> P-C4H9 + A-C3H5 { A = 1.08E+03 n = 3.77 E = 278.43 } HP22f: C7H14 + H -> C7H13 + H2 { A = 3.70E+13 n = .00 E = 16.32 } HP23 : C7H14 + OH -> C7H13 + H2O { A = 3.00E+13 n = .00 E = 5.15 } HP24 : C7H14 + OH -> CH3CHO + C5H11 { A = 9.87E+22 n = -3.62 E = 12.15 } HP25 : C7H14 + OH -> C2H5 + HCO + P-C4H9 { A = 2.07E+16 n = -1.65 E = -7.63 } # Reactions of C7H13 HP26 : C7H13 -> A-C3H5 + P-C4H8 { A = 2.50E+13 n = .00 E = 188.28 } HP27 : C7H13 -> C4H7 + C3H6 { A = 2.50E+13 n = .00 E = 188.28 } # Reactions of C5H11 HP28 : C5H11 -> C2H4 + N-C3H7 { A = 7.46E+21 n = -2.61 E = 134.00 } HP29 : C5H11 -> H + C5H10 { A = 8.46E+14 n = -0.47 E = 157.39 } HP30 : C5H10 + H -> C5H11 { A = 7.10E+12 n = 0.12 E = 6.11 } HP31 : C5H11 -> C3H6 + C2H5 { A = 3.15E-19 n = 8.84 E = 29.73 } # Reactions of C5H10 HP32 : C5H10 -> C2H5 + A-C3H5 { A = 9.17E+20 n = -1.63 E = 309.57 } HP33 : C5H10 + H -> C5H9 + H2 { A = 2.80E+13 n = .00 E = 16.74 } HP34 : C5H10 + O -> C5H9 + OH { A = 2.54E+05 n = 2.56 E = -4.73 } HP35 : C5H10 + OH -> C5H9 + H2O { A = 5.12E+06 n = 2.00 E = -1.25 } # Reactions of C5H9 # Already done in NC12 chemistry # Reactions of P-C4H9 HP36 : P-C4H9 -> P-C4H8 + H { A = 8.61E+17 n = -1.40 E = 162.80 } HP37 : P-C4H8 + H -> P-C4H9 { A = 7.68E+12 n = 0.11 E = 6.19 } HP38 : P-C4H9 -> C2H5 + C2H4 { A = 8.39E+14 n = -0.64 E = 112.57 } HP39 : P-C4H9 -> C3H6 + CH3 { A = 1.00E+31 n = -5.43 E = 177.85 } # Reactions of P-C4H8 reactions HP40 : P-C4H8 -> A-C3H5 + CH3 { A = 5.00E+15 n = .00 E = 297.06 } HP41 : P-C4H8 + H -> C4H7 + H2 { A = 5.00E+13 n = .00 E = 16.32 } HP42 : P-C4H8 + OH -> C4H7 + H2O { A = 2.25E+13 n = .00 E = 9.28 } HP43 : P-C4H8 + O2 -> C4H7 + HO2 { A = 2.70E+13 n = .00 E = 138.91 } HP44 : P-C4H8 + HO2 -> C4H7 + H2O2 { A = 1.40E+12 n = .00 E = 62.34 } HP45 : P-C4H8 + CH3 -> C4H7 + CH4 { A = 1.00E+11 n = .00 E = 30.54 } HP46 : C4H7 + H -> P-C4H8 { A = 5.00E+13 n = .00 E = .00 } HP47 : C4H7 + HO2 -> P-C4H8 + O2 { A = 3.00E+11 n = .00 E = .00 } HP48 : P-C4H8 + O -> CH3CHO + C2H4 { A = 1.30E+13 n = .00 E = 3.56 } HP49 : P-C4H8 + O -> C2H5 + CH3 + CO { A = 1.30E+13 n = .00 E = 3.56 } HP50 : P-C4H8 + O -> C3H6 + CH2O { A = 7.23E+05 n = 2.34 E = -4.39 } HP51 : P-C4H8 + O -> C2H5 + HCO + T-CH2 { A = 1.30E+13 n = .00 E = 3.56 } HP52 : P-C4H8 + OH -> N-C3H7 + CH2O { A = 1.00E+12 n = .00 E = .00 } HP53 : P-C4H8 + OH -> C2H6 + CH3 + CO { A = 5.00E+11 n = .00 E = .00 } HP54 : P-C4H8 + OH -> C2H5 + CH3 + HCO { A = 1.00E+12 n = .00 E = .00 } HP55 : P-C4H8 + OH -> C2H5 + CH3CHO { A = 1.00E+12 n = .00 E = .00 } # Reactions of C3H7CHO HP56 : C3H7CHO + H -> N-C3H7 + CO + H2 { A = 4.00E+13 n = .00 E = 17.57 } HP57 : C3H7CHO + OH -> N-C3H7 + CO + H2O { A = 2.69E+10 n = .76 E = -1.42 } HP58 : C3H7CHO + O2 -> N-C3H7 + CO + HO2 { A = 2.00E+13 n = .50 E = 176.57 } HP59 : C3H7CHO + CH3 -> N-C3H7 + CO + CH4 { A = 1.70E+12 n = .00 E = 35.31 } HP60 : C3H7CHO + HO2 -> N-C3H7 + CO + H2O2 { A = 2.80E+12 n = .00 E = 56.90 } # Reactions of C4H7 # Revised C4H7 system - Exp. + Calc. # Shestov, Popov, Slagle & Knyazev 2005 # Ismail, Georgievskii, Taatjes, et al. 2007 # Rates fitted at P=1.33bar HP61f: C4H7 -> C4H6 + H { A = 5.01E+31 n = -5.90 E = 162.29 } HP62f: C2H4 + C2H3 -> C4H7 { A = 1.88E+06 n = 1.84 E = 12.80 } HP63 : C4H7 + H -> C4H6 + H2 { A = 3.16E+13 n = .00 E = .00 } HP64 : C4H7 + O2 -> C4H6 + HO2 { A = 1.00E+09 n = .00 E = .00 } HP65 : C4H7 + CH3 -> C4H6 + CH4 { A = 8.00E+12 n = .00 E = .00 } HP66 : C4H7 + C2H5 -> C4H6 + C2H6 { A = 3.98E+12 n = .00 E = .00 } HP67 : C4H7 + A-C3H5 -> C4H6 + C3H6 { A = 6.31E+12 n = .00 E = .00 } HP68 : C4H7 + HO2 -> C4H7O + OH { A = 7.00E+12 n = .00 E = -4.18 } HP69 : C4H7 + CH3O2 -> C4H7O + CH3O { A = 7.00E+12 n = .00 E = -4.18 } # Reactions of C4H7O HP70 : C4H7O -> CH3CHO + C2H3 { A = 7.94E+14 n = .00 E = 79.50 } HP71 : C4H7O -> C2H3CHO + CH3 { A = 7.94E+14 n = .00 E = 79.50 } # ------------------- LOW TEMPERATURE -------------------- # # ---------------------- 5 Species ----------------------- # # -------------------- 11 Reactions ---------------------- # /* Commented for now # Formation of ROO HP80: C7H15 + O2 -> C7H15O2 { A = 1.68E+13 n = -0.11 E = 1.01 } HP81: C7H15O2 -> C7H15 + O2 { A = 1.92E+22 n = -2.11 E = 156.08 } HP82: C7H15O2 -> C7H14OOH { A = 1.88E+05 n = 1.68 E = 79.51 } # Reactions of QOOH HP83: C7H14OOH -> C7H15O2 { A = 7.64E+05 n = 0.91 E = 25.45 } HP84: C7H14OOH -> C7H14 + HO2 { A = 5.85E+03 n = 2.40 E = 64.08 } HP85: C7H14OOH -> C7H14O + OH { A = 3.97E-10 n = 5.69 E = 1.57 } HP86: C7H14OOH + O2 -> C7H15O4 { A = 1.51E+13 n = -0.09 E = 0.53 } # Reactions of O2QOOH HP87: C7H15O4 -> C7H14OOH + O2 { A = 1.71E+22 n = -2.13 E = 155.32 } HP88: C7H15O4 -> OC7H13OOH + OH { A = 4.25E+10 n = -0.11 E = 81.48 } # Reactions of OQ'OOH # all products lumped HP89: OC7H13OOH -> N-C3H7 + CH3CHO + CH2CO + OH { A = 3.26E+09 n = 1.93 E = 161.11 } # Reactions of QO # all products lumped HP90: C7H14O + OH -> C5H11 + CH2CO + H2O { A = 3.68E+12 n = .00 E = .00 } */ #==========================================================================# # # # Redcued iso-Octane mechanism # # Lawrence Livermore Iso-Octane Mechanism - ver 2e # # # # "A Comprehensive Modeling Study of iso-Octane Oxidation" # # Curran, H. J., Gaffuri, P., Pitz, W. J., and Westbrook, C. K. # # Combustion and Flame 129:253-280 (2002). # # # # UCRL-WEB-204236 - Review and release date: May 19, 2004. # # # #==========================================================================# # ------------------- HIGH TEMPERATURE -------------------- # # ---------------------- 15 Species ----------------------- # # --------------------- 73 Reactions ---------------------- # # Reactions of I-C8H18 IC00 : I-C8H18 -> Y-C7H15 + CH3 { A = 1.02E+49 n = -9.38 E = 404.10 } IC01 : I-C8H18 -> I-C4H8 + I-C3H7 + CH3 { A = 5.75E+49 n = -9.66 E = 410.20 } IC02 : I-C8H18 -> 2 T-C4H9 { A = 1.94E+57 n =-11.84 E = 414.13 } IC03 : I-C8H18 + H -> C-C8H17 + H2 { A = 5.15E+01 n = 3.92 E = 10.16 } IC04 : I-C8H18 + O -> C-C8H17 + OH { A = 1.25E+04 n = 3.07 E = 5.82 } IC05 : I-C8H18 + OH -> C-C8H17 + H2O { A = 1.03E+07 n = 1.99 E = -1.19 } IC06 : I-C8H18 + O2 -> C-C8H17 + HO2 { A = 1.03E+11 n = 0.84 E = 196.29 } IC07 : I-C8H18 + CH3 -> C-C8H17 + CH4 { A = 1.14E-18 n = 9.25 E = -8.89 } IC08 : I-C8H18 + HO2 -> C-C8H17 + H2O2 { A = 9.85E+10 n = 0.73 E = 70.89 } # Reduced by 2 IC09 : I-C8H18 + CH3O2 -> C-C8H17 + CH3O + OH { A = 4.93E+10 n = 0.73 E = 70.89 } # Reactions of C-C8H17 IC10 : C-C8H17 -> I-C4H8 + T-C4H9 { A = 4.28E+22 n = -2.81 E = 127.70 } IC11 : C-C8H17 -> Y-C7H14 + CH3 { A = 2.55E+39 n = -7.47 E = 189.48 } IC12 : C-C8H17 -> I-C4H8 + CH3 + C3H6 { A = 4.22E+24 n = -3.34 E = 158.66 } IC13 : C-C8H17 + HO2 -> D-C8H17O + OH { A = 7.00E+12 n = .00 E = -4.18 } IC14 : C-C8H17 + CH3O2 -> D-C8H17O + CH3O { A = 7.00E+12 n = .00 E = -4.18 } # Reactions of D-C8H17O IC15 : D-C8H17O -> I-C4H8 + CH3 + CH3COCH3 { A = 1.33E+23 n = -2.98 E = 64.44 } IC16 : D-C8H17O -> T-C4H9 + I-C3H7 + HCO { A = 7.95E+33 n = -6.00 E = 97.57 } IC17 : D-C8H17O -> Y-C7H15 + CH2O { A = 2.69E+20 n = -2.08 E = 62.99 } # Reactions of Y-C7H15 IC18 : Y-C7H14 + H -> Y-C7H15 { A = 7.92E+16 n = -1.01 E = 15.98 } IC19 : Y-C7H15 -> Y-C7H14 + H { A = 1.83E+17 n = -0.90 E = 165.71 } IC20 : Y-C7H15 -> I-C4H8 + I-C3H7 { A = 1.94E+18 n = -1.49 E = 136.77 } IC21 : Y-C7H15 -> T-C4H9 + C3H6 { A = 1.12E-44 n = 15.73 E = -65.59 } # Reactions of Y-C7H14 IC22 : Y-C7H14 -> I-C4H7 + I-C3H7 { A = 6.53E+59 n =-12.99 E = 394.69 } IC23 : Y-C7H14 -> T-C4H9 + A-C3H5 { A = 2.09E+65 n =-14.94 E = 384.52 } IC24 : Y-C7H14 + H -> X-C7H13 + H2 { A = 2.38E-13 n = 7.67 E = -47.65 } IC25 : X-C7H13 + H2 -> Y-C7H14 + H { A = 3.93E+06 n = 2.36 E = 92.29 } IC26 : Y-C7H14 + OH -> X-C7H13 + H2O { A = 7.76E-09 n = 6.18 E = -41.33 } IC27 : X-C7H13 + H2O -> Y-C7H14 + OH { A = 1.92E+05 n = 2.76 E = 159.33 } # Reactions of X-C7H13 IC28 : X-C7H13 + HO2 -> I-C3H5CHO + I-C3H7 + OH { A = 1.00E+13 n = .00 E = .00 } # Reactions of T-C4H9O IC29 : T-C4H9O -> I-C3H7 + HCO + H { A = 1.78E+39 n = -7.30 E = 156.05 } IC30 : T-C4H9O -> CH2O + I-C3H7 { A = 7.25E+39 n = -7.59 E = 140.03 } IC31 : T-C4H9O -> CH3COCH3 + CH3 { A = 3.09E+13 n = 0.03 E = 58.87 } # Reactions of T-C4H9 IC32 : T-C4H9 -> C3H6 + CH3 { A = 1.34E+71 n =-17.29 E = 263.24 } IC33 : T-C4H9 -> H + I-C4H8 { A = 7.84E+45 n = -9.64 E = 226.42 } IC34 : I-C4H8 + H -> T-C4H9 { A = 2.14E+41 n = -8.43 E = 60.54 } IC35 : T-C4H9 + HO2 -> T-C4H9O + OH { A = 7.00E+12 n = .00 E = -4.18 } IC36 : T-C4H9 + CH3O2 -> T-C4H9O + CH3O { A = 7.00E+12 n = .00 E = -4.18 } # Reactions of I-C4H8 IC37 : I-C4H8 -> T-C3H5 + CH3 { A = 1.92E+66 n =-14.22 E = 535.97 } IC38f: I-C4H8 -> I-C4H7 + H { A = 3.07E+55 n =-11.49 E = 478.23 } IC40 : I-C4H8 + H -> C3H6 + CH3 { A = 5.68E+33 n = -5.72 E = 83.68 } IC41f: I-C4H8 + H -> I-C4H7 + H2 { A = 3.40E+05 n = 2.50 E = 10.43 } IC42 : I-C4H8 + O -> I-C4H7 + OH { A = 1.21E+11 n = 0.70 E = 31.94 } IC43 : I-C4H8 + OH -> I-C4H7 + H2O { A = 5.20E+06 n = 2.00 E = -1.25 } IC44 : I-C4H8 + CH3 -> I-C4H7 + CH4 { A = 4.42E+00 n = 3.50 E = 23.74 } IC45 : I-C4H8 + HO2 -> I-C4H7 + H2O2 { A = 1.93E+04 n = 2.60 E = 58.20 } IC46 : I-C4H8 + CH3O2 -> I-C4H7 + CH3O + OH { a = 1.93E+04 n = 2.60 E = 58.20 } IC47 : I-C4H8 + O -> I-C3H7 + HCO { A = 1.58E+07 n = 1.76 E = -5.09 } IC48 : I-C4H8 + O -> CH2CO + 2 CH3 { A = 3.33E+07 n = 1.76 E = 0.32 } # Reactions of I-C4H7O IC49 : I-C4H7O -> T-C3H5 + CH2O { A = 1.01E+18 n = -1.45 E = 129.04 } IC50 : I-C4H7O -> I-C3H5CHO + H { A = 5.00E+13 n = .00 E = 121.75 } IC51 : I-C4H7O + O2 -> I-C3H5CHO + HO2 { A = 3.00E+10 n = .00 E = 6.90 } # Reactions of I-C4H7 IC52 : I-C4H7 -> A-C3H4 + CH3 { A = 1.23E+47 n = -9.74 E = 310.70 } # From C2H5 + HO2 # Ludwig et al. .2006 IC57 : I-C4H7 + HO2 -> I-C4H7O + OH { A = 3.10E+13 n = .00 E = .00 } # Change of products IC53 : I-C4H7 + O -> I-C4H7O { A = 6.03E+13 n = .00 E = .00 } IC54 : I-C4H7 + O2 -> I-C3H5CHO + OH { A = 2.47E+13 n = -0.45 E = 96.32 } IC55 : I-C4H7 + O2 -> CH2CO + CH2O + CH3 { A = 7.14E+15 n = -1.21 E = 88.07 } IC56 : I-C4H7 + O2 -> A-C3H4 + CH2O + OH { A = 7.29E+29 n = -5.71 E = 89.75 } IC58 : I-C4H7 + CH3O2 -> I-C4H7O + CH3O { A = 7.00E+12 n = .00 E = -4.18 } # Reactions of I-C3H5CHO IC59 : I-C3H5CHO + H -> T-C3H5 + CO + H2 { A = 2.60E+12 n = .00 E = 10.88 } IC60 : I-C3H5CHO + O -> T-C3H5 + CO + OH { A = 7.18E+12 n = .00 E = 5.81 } IC61 : I-C3H5CHO + OH -> T-C3H5 + CO + H2O { A = 2.69E+10 n = 0.76 E = -1.42 } IC62 : I-C3H5CHO + HO2 -> T-C3H5 + CO + H2O2 { A = 1.00E+12 n = .00 E = 49.87 } IC63 : I-C3H5CHO + CH3 -> T-C3H5 + CO + CH4 { A = 3.98E+12 n = .00 E = 36.40 } # Reactions of CH3COCH3 IC69 : CH3COCH3 + H -> CH2CO + CH3 + H2 { A = 5.63E+07 n = 2.00 E = 32.22 } IC70 : CH3COCH3 + O -> CH2CO + CH3 + OH { A = 1.13E+14 n = .00 E = 32.84 } IC71 : CH3COCH3 + OH -> CH2CO + CH3 + H2O { A = 1.05E+10 n = 0.97 E = 6.64 } IC72 : CH3COCH3 + HO2 -> CH2CO + CH3 + H2O2 { A = 1.70E+13 n = .00 E = 85.61 } #==========================================================================# # # # Reduced N-Dodecane mechanism # # Lawrence Livermore n-Alkanes Mechanism - ver 2 # # # # "A Detailed Chemical Kinetic Reaction Mechanism for # # n-Alkane Hydrocarbons from n-Octane to n-Hexadecane" # # C. K. Westbrook, W. J. Pitz, O. Herbinet, H. J. Curran and E. J. Silke # # Combustion and Flame 156:181-199 (2009). # # # # LLNL-MI-407455 - version dated 2008-09-02 C.K. Westbrook # # # #==========================================================================# # ------------------- HIGH TEMPERATURE -------------------- # # ---------------------- 15 Species ----------------------- # # --------------------- 78 Reactions ---------------------- # # Reactions of N-C12H26 DD01: N-C12H26 -> C10H21 + C2H5 { A = 2.72E+25 n = -2.45 E = 368.07 } DD02: N-C12H26 -> C9H19 + N-C3H7 { A = 8.05E+22 n = -1.97 E = 365.31 } DD03: N-C12H26 -> C8H17 + P-C4H9 { A = 1.21E+24 n = -2.07 E = 369.64 } DD04: N-C12H26 -> C7H15 + C5H11 { A = 1.13E+24 n = -2.06 E = 369.58 } DD05: N-C12H26 -> C6H13 + C6H13 { A = 2.59E+24 n = -2.12 E = 369.69 } DD06: N-C12H26 + H -> C12H25 + H2 { A = 6.25E+06 n = 2.51 E = 18.43 } DD07: N-C12H26 + O -> C12H25 + OH { A = 3.97E+05 n = 2.76 E = 9.19 } DD08: N-C12H26 + OH -> C12H25 + H2O { A = 8.74E+08 n = 1.55 E = 0.52 } DD09: N-C12H26 + O2 -> C12H25 + HO2 { A = 1.05E+14 n = 0.10 E = 209.77 } DD10: N-C12H26 + HO2 -> C12H25 + H2O2 { A = 2.86E+13 n = 0.11 E = 73.93 } # Reactions of C12H25 DD11: C12H25 -> H + C12H24 { A = 5.67E+12 n = 0.13 E = 148.86 } DD12: C12H25 -> C2H5 + C10H20 { A = 1.81E+18 n = -1.87 E = 125.55 } DD13: C12H25 -> N-C3H7 + C9H18 { A = 4.15E+16 n = -1.54 E = 127.35 } DD14: C12H25 -> P-C4H9 + C8H16 { A = 5.78E+17 n = -1.68 E = 130.27 } DD15: C12H25 -> C5H11 + C7H14 { A = 7.51E+17 n = -1.71 E = 130.58 } DD16: C12H25 -> C6H13 + C6H12 { A = 1.09E+18 n = -1.67 E = 131.44 } DD17: C12H25 -> C7H15 + C5H10 { A = 8.95E+16 n = -1.45 E = 126.69 } DD18: C12H25 -> C8H17 + P-C4H8 { A = 4.26E+18 n = -1.90 E = 128.40 } DD19: C12H25 -> C9H19 + C3H6 { A = 1.17E+17 n = -1.40 E = 126.59 } DD20: C12H25 -> C10H21 + C2H4 { A = 7.57E+19 n = -2.34 E = 134.58 } # Reactions of C12H24 DD21: C12H24 -> C9H19 + A-C3H5 { A = 9.53E+15 n = -0.18 E = 298.01 } DD22: C12H24 -> C8H15 + P-C4H9 { A = 1.51E+13 n = 0.52 E = 294.52 } DD23: C12H24 -> C7H13 + C5H11 { A = 2.08E+15 n = -0.04 E = 297.23 } DD24: C12H24 -> C5H9 + C7H15 { A = 1.50E+15 n = -0.02 E = 297.10 } DD25: C12H24 -> C4H7 + C8H17 { A = 1.87E+15 n = 0.04 E = 296.85 } DD26: C12H24 + H -> C12H23 + H2 { A = 3.70E+13 n = .00 E = 16.32 } DD27: C12H24 + OH -> C12H23 + H2O { A = 3.00E+13 n = .00 E = 5.15 } # Reactions of C12H23 DD28: C12H23 -> C2H3 + C10H20 { A = 1.00E+13 n = .00 E = 188.28 } DD29: C12H23 -> A-C3H5 + C9H18 { A = 1.00E+13 n = .00 E = 188.28 } DD30: C12H23 -> C4H7 + C8H16 { A = 1.00E+13 n = .00 E = 188.28 } DD31: C12H23 -> C5H9 + C7H14 { A = 1.00E+13 n = .00 E = 188.28 } DD32: C12H23 -> C7H13 + C5H10 { A = 1.00E+13 n = .00 E = 188.28 } DD33: C12H23 -> C8H15 + P-C4H8 { A = 1.00E+13 n = .00 E = 188.28 } DD34: C12H23 -> C9H17 + C3H6 { A = 1.00E+13 n = .00 E = 188.28 } DD35: C12H23 -> C10H19 + C2H4 { A = 1.00E+13 n = .00 E = 188.28 } # Reactions of C10H21 DD36: C10H21 -> C10H20 + H { A = 3.67E+11 n = 0.50 E = 146.74 } DD37: C10H21 -> C8H17 + C2H4 { A = 4.76E+27 n = -4.55 E = 143.50 } DD38: C10H21 -> C7H15 + C3H6 { A = 1.78E+02 n = 3.07 E = 109.00 } DD39: C10H21 -> C8H16 + C2H5 { A = 8.43E+16 n = -1.69 E = 121.15 } # Reactions of C10H20 DD40: C10H20 -> C7H15 + A-C3H5 { A = 1.00E+16 n = .00 E = 297.06 } DD41: C10H20 + H -> C10H19 + H2 { A = 3.70E+13 n = .00 E = 16.32 } DD42: C10H20 + OH -> C10H19 + H2O { A = 3.00E+13 n = .00 E = 5.15 } # Reactions of C10H19 DD43: C10H19 -> C8H15 + C2H4 { A = 1.00E+13 n = .00 E = 188.28 } DD44: C10H19 -> C7H13 + C3H6 { A = 1.00E+13 n = .00 E = 188.28 } DD45: C10H19 -> C5H9 + C5H10 { A = 1.00E+13 n = .00 E = 188.28 } DD46: C10H19 -> C4H7 + C6H12 { A = 1.00E+13 n = .00 E = 188.28 } DD47: C10H19 -> A-C3H5 + C7H14 { A = 1.00E+13 n = .00 E = 188.28 } DD48: C10H19 -> C2H3 + C8H16 { A = 1.00E+13 n = .00 E = 188.28 } # Reactions of C9H19 DD49: C9H19 -> C9H18 + H { A = 3.31E+13 n = -0.12 E = 149.87 } DD50: C9H19 -> C7H15 + C2H4 { A = 2.56E+19 n = -2.00 E = 131.09 } DD51: C9H19 -> C6H13 + C3H6 { A = 1.04E+11 n = 0.43 E = 126.05 } DD52: C9H19 -> C7H14 + C2H5 { A = 3.79E+31 n = -5.99 E = 151.33 } # Reactions of C9H18 DD53: C9H18 -> C6H13 + A-C3H5 { A = 6.42E+15 n = .05 E = 296.58 } DD54: C9H18 + H -> C9H17 + H2 { A = 3.70E+13 n = .00 E = 16.32 } DD55: C9H18 + OH -> C9H17 + H2O { A = 3.00E+13 n = .00 E = 5.15 } # Reactions of C9H17 DD56: C9H17 -> C2H3 + C7H14 { A = 1.00E+13 n = .00 E = 188.28 } DD57: C9H17 -> A-C3H5 + C6H12 { A = 1.00E+13 n = .00 E = 188.28 } DD58: C9H17 -> C4H7 + C5H10 { A = 1.00E+13 n = .00 E = 188.28 } DD59: C9H17 -> C5H9 + P-C4H8 { A = 1.00E+13 n = .00 E = 188.28 } DD60: C9H17 -> C7H13 + C2H4 { A = 1.00E+13 n = .00 E = 188.28 } # Reactions of C8H17 DD61: C8H17 -> C8H16 + H { A = 1.66E+12 n = 0.29 E = 148.11 } DD62: C8H17 -> C6H13 + C2H4 { A = 8.61E+24 n = -3.68 E = 140.90 } DD63: C8H17 -> C6H12 + C2H5 { A = 9.98E+32 n = -6.34 E = 154.08 } DD64: C8H17 -> C5H11 + C3H6 { A = 4.35E+12 n = -0.08 E = 128.41 } # Reactions of C8H16 DD65: C8H16 -> C5H11 + A-C3H5 { A = 1.57E+13 n = 0.71 E = 285.22 } DD66: C8H16 + H -> C8H15 + H2 { A = 3.70E+13 n = .00 E = 16.32 } DD67: C8H16 + OH -> C8H15 + H2O { A = 3.00E+13 n = .00 E = 5.15 } # Reactions of C8H15 DD68: C8H15 -> C5H9 + C3H6 { A = 1.00E+13 n = .00 E = 188.28 } DD69: C8H15 -> C4H7 + P-C4H8 { A = 1.00E+13 n = .00 E = 188.28 } DD70: C8H15 -> A-C3H5 + C5H10 { A = 1.00E+13 n = .00 E = 188.28 } DD71: C8H15 -> C2H3 + C6H12 { A = 1.00E+13 n = .00 E = 188.28 } # Reactions of C6H13 DD72: C6H13 -> C6H12 + H { A = 4.94E+15 n = -0.71 E = 157.48 } DD73: C6H13 -> P-C4H9 + C2H4 { A = 3.76E+20 n = -2.16 E = 128.65 } DD74: C6H13 -> P-C4H8 + C2H5 { A = 4.07E+10 n = 0.34 E = 123.24 } DD75: C6H13 -> N-C3H7 + C3H6 { A = 1.50E+06 n = 1.94 E = 114.77 } # Reactions of C6H12 DD76: C6H12 -> N-C3H7 + A-C3H5 { A = 1.00E+16 n = .00 E = 297.06 } DD77: C6H12 + H -> C3H6 + A-C3H5 + H2 { A = 3.70E+13 n = .00 E = 16.32 } DD78: C6H12 + OH -> C3H6 + A-C3H5 + H2O { A = 3.00E+13 n = .00 E = 5.15 } # -------------------- LOW TEMPERATURE -------------------- # # ----------------------- 10 Species ---------------------- # # ---------------------- 21 Reactions --------------------- # /* # Reactions of C12H25O2 # Backward rate reduced (x1/6) # to mimic lumping of peroxy species DD80: C12H25 + O2 -> C12H25O2 { A = 9.52E+12 n = -0.04 E = 0.23 } DD81: C12H25O2 -> C12H25 + O2 { A = 1.52E+22 n = -2.31 E = 156.59 } DD82: C12H25O2 -> C12H24OOH { A = 1.13E+06 n = 1.46 E = 80.17 } DD83: C12H24OOH -> C12H25O2 { A = 4.47E+21 n = -3.86 E = 58.11 } # Reactions of C12H24OOH DD84: C12H24OOH -> C12H24 + HO2 { A = 2.21E+14 n = -0.81 E = 84.74 } DD85: C12H24OOH -> C12H24O + OH { A = 3.25E-11 n = 5.92 E = -7.84 } DD86: C12H24OOH + O2 -> C12H25O4 { A = 1.32E+13 n = -0.08 E = 0.47 } # Reactions of C12H25O4 DD87: C12H25O4 -> C12H24OOH + O2 { A = 1.92E+23 n = -2.42 E = 157.60 } DD88: C12H25O4 -> C12H24O3 + OH { A = 1.28E+07 n = 0.89 E = 72.18 } # Reactions of C12H24O3 # lump all decomposition pathways DD89: C12H24O3 -> C8H17 + CH3CHO + CH2CO + OH { A = 8.95E+14 n = 0.32 E = 171.10 } # Reactions of C12H24O # lump all decomposition pathways DD90: C12H24O + OH -> C8H17 + C2H4 + CH2CO + H2O{ A = 3.09E+13 n = -0.27 E = 1.61 } # Reactions of C8H17O2 DD91: C8H17 + O2 -> C8H17O2 { A = 1.65E+22 n = -2.85 E = 19.78 } DD92: C8H17O2 -> C8H17 + O2 { A = 2.48E+21 n = -1.94 E = 150.73 } DD93: C8H17O2 -> C8H16OOH { A = 1.11E+06 n = 1.40 E = 79.77 } # Reactions of C8H16OOH DD94: C8H16OOH -> C8H16O + OH { A = 3.07E+02 n = 2.15 E = 24.57 } DD95: C8H16OOH -> C8H16 + HO2 { A = 5.11E+06 n = 1.40 E = 70.08 } DD96: C8H16OOH + O2 -> C8H17O4 { A = 1.16E+11 n = 0.53 E = -3.58 } # Reactions of C8H17O4/C8H16O3 DD97: C8H17O4 -> C8H16OOH + O2 { A = 1.37E+23 n = -2.37 E = 157.49 } DD98: C8H17O4 -> C8H16O3 + OH { A = 9.98E+06 n = 1.02 E = 83.92 } DD99: C8H16O3 -> P-C4H9 + CH3CHO + CH2CO + OH { A = 4.44E+32 n = -4.98 E = 207.98 } LP8046: C8H16O + OH -> C6H13 + CH2CO + H2O { A = 3.09E+13 n = -0.27 E = 1.61 } */ #==========================================================================# # # # Reduced Methyl-CycloHexane mechanism # # # # "Modeling and Experimental Investigation of Methylcyclohexane # # Ignition in a Rapid Compression Machine" # # Pitz, Naik, Mhaolduin, Westbrook, Curran, Orme, Simmie # # Proc. Comb. Inst. 31:267-275 (2007) # # # # LLNL-MI-407571 - version 1u2 dated 5-9-2006 W.J. Pitz # # # #==========================================================================# # ------------------- HIGH TEMPERATURE -------------------- # # ---------------------- 16 Species ----------------------- # # --------------------- 54 Reactions ---------------------- # # Reactions of MCH-C7H14 MC00: MCH-C7H14 -> C-C6H11 + CH3 { A = 1.44E+23 n = -1.78 E = 369.57 } MC01: MCH-C7H14 + H -> MCHR-C7H13 + H2 { A = 3.60E+06 n = 2.48 E = 16.52 } MC02: MCH-C7H14 + O -> MCHR-C7H13 + OH { A = 1.72E+06 n = 2.52 E = 9.83 } MC03: MCH-C7H14 + OH -> MCHR-C7H13 + H2O { A = 2.44E+08 n = 1.60 E = -1.02 } MC04: MCH-C7H14 + O2 -> MCHR-C7H13 + HO2 { A = 7.62E+13 n = 0.04 E = 206.31 } MC05: MCH-C7H14 + CH3 -> MCHR-C7H13 + CH4 { A = 2.18E-04 n = 4.84 E = 12.67 } MC06: MCH-C7H14 + HO2 -> MCHR-C7H13 + H2O2 { A = 4.84E+03 n = 2.87 E = 52.63 } MC07: MCH-C7H14 + CH3O -> MCHR-C7H13 + CH3OH { A = 5.98E+11 n = 0.03 E = 18.42 } MC08: MCH-C7H14 + CH3O2-> MCHR-C7H13 + CH3O + OH{ A = 4.85E+03 n = 2.87 E = 56.81 } # Reactions of MCHR-C7H13 MC09: MCHR-C7H13 -> C-C6H10 + CH3 { A = 1.00E+55 n =-12.09 E = 234.12 } MC10: MCHR-C7H13 -> MCHE-C7H12 + H { A = 4.17E+17 n = -1.45 E = 161.01 } MC11: MCHR-C7H13 -> AF-C7H13 { A = 7.88E+14 n = -0.02 E = 122.35 } MC12: AF-C7H13 -> C2H4 + AD-C5H9 { A = 4.15E+56 n =-11.43 E = 298.05 } MC13: AF-C7H13 -> C2H4 + C5H9 { A = 1.17E+41 n = -7.96 E = 177.22 } MC14: AF-C7H13 -> C2H5 + I-C5H8 { A = 4.17E+58 n =-13.08 E = 244.78 } MC15: AF-C7H13 -> C2H5 + C5H8 { A = 1.82E+37 n = -6.64 E = 188.80 } MC16: AF-C7H13 -> C3H6 + C4H7 { A = 9.08E+84 n =-20.90 E = 280.01 } MC17: AF-C7H13 -> C4H6 + N-C3H7 { A = 4.09E+34 n = -6.03 E = 199.03 } MC18: AF-C7H13 -> C6H10 + CH3 { A = 8.32E+68 n =-16.56 E = 269.26 } MC19: MCHR-C7H13 + O2 -> MCHE-C7H12 + HO2 { A = 3.26E+11 n = 0.16 E = 32.04 } # Reactions of MCHE-C7H12 MC20: MCHE-C7H12 + H -> MCHJE-C7H11 + H2 { A = 1.00E+14 n = .00 E = 16.32 } MC21: MCHE-C7H12 + OH -> MCHJE-C7H11 + H2O { A = 4.50E+13 n = .00 E = 9.28 } MC22: MCHE-C7H12 + O2 -> MCHJE-C7H11 + HO2 { A = 5.40E+13 n = .00 E = 159.83 } MC23: MCHE-C7H12 + HO2 -> MCHJE-C7H11 + H2O2 { A = 2.80E+12 n = .00 E = 62.34 } # Reactions of MCHJE-C7H11 MC24: MCHJE-C7H11 -> C5H8 + C2H3 { A = 1.34E+15 n = 0.02 E = 123.00 } MC25: MCHJE-C7H11 + O2 -> MCHDE-C7H10 + HO2 { A = 6.00E+13 n = .00 E = 64.73 } MC26: MCHJE-C7H11 + HO2 -> MCHDE-C7H10 + H2O2 { A = 1.32E+04 n = 2.50 E = -6.23 } # Reactions of MCHDE-C7H10 MC27: MCHDE-C7H10 + OH -> MCHJDE-C7H9 + H2O { A = 2.25E+13 n = .00 E = 5.09 } MC28: MCHDE-C7H10 + HO2 -> MCHJDE-C7H9 + H2O2 { A = 1.40E+12 n = .00 E = 58.16 } # Reactions of MCHJDE-C7H9 MC29: MCHJDE-C7H9 -> A1-C6H6 + CH3 { A = 1.01E+21 n = -2.16 E = 47.94 } MC30: MCHJDE-C7H9 -> A1CH3-C7H8 + H { A = 1.54E+18 n = -0.98 E = 51.57 } # Reactions of C6H11 MC31: C-C6H11 -> C-C6H10 + H { A = 1.84E+17 n = -1.23 E = 161.51 } MC32: C-C6H11 -> C6H11 { A = 2.58E+14 n = -0.44 E = 49.79 } MC33: C6H11 -> C3H6 + A-C3H5 { A = 2.50E+13 n = .00 E = 188.28 } MC34: C6H11 -> C2H5 + C4H6 { A = 1.48E+13 n = 0.62 E = 168.67 } MC35: C6H11 -> C6H10 + H { A = 7.42E+11 n = 0.77 E = 198.76 } # Reactions of C6H10 MC36: C-C6H10 -> C4H6 + C2H4 { A = 3.64E+62 n =-13.80 E = 385.05 } MC37: C-C6H10 + H -> C-C6H9 + H2 { A = 8.41E+03 n = 3.08 E = 1.76 } MC38: C-C6H10 + O -> C-C6H9 + OH { A = 1.09E+06 n = 2.53 E = 6.30 } MC39: C-C6H10 + OH -> C-C6H9 + H2O { A = 9.72E+05 n = 2.33 E = -5.69 } MC40: C-C6H10 + CH3 -> C-C6H9 + CH4 { A = 3.59E+00 n = 3.50 E = 17.83 } MC41: C-C6H10 + HO2 -> C-C6H9 + H2O2 { A = 1.60E+13 n = .00 E = 66.94 } MC42: C6H10 + H -> L-C6H9 + H2 { A = 6.75E+05 n = 2.36 E = 0.87 } MC43: C6H10 + O -> L-C6H9 + OH { A = 1.32E+06 n = 2.43 E = 5.06 } MC44: C6H10 + OH -> L-C6H9 + H2O { A = 5.53E+04 n = 2.64 E = -8.03 } # Reactions of C6H9 MC45: C-C6H9 -> L-C6H9 { A = 4.45E-20 n = 9.43 E = 38.52 } MC46: C-C6H9 -> C-C6H8 + H { A = 2.57E-04 n = 4.94 E = 148.14 } MC47: L-C6H9 -> N-C4H5 + C2H4 { A = 2.60E+35 n = -5.85 E = 278.98 } MC48: L-C6H9 -> C4H6 + C2H3 { A = 1.60E+13 n = 0.36 E = 199.31 } MC50: L-C6H9 -> L-C6H8 + H { A = 2.31E+21 n = -2.23 E = 200.41 } # Reactions of C6H8 MC51: C-C6H8 -> A1-C6H6 + H2 { A = 3.74E+07 n = .00 E = 123.67 } MC52: C-C6H8 -> C-C6H7 + H { A = 8.41E+08 n = .00 E = 162.14 } MC53: H + C-C6H7 -> C-C6H8 { A = 1.61E+13 n = 0.33 E = -16.43 } #MC54: C-C6H8 -> CH3 + C5H5 { A = 1.33E+09 n = .00 E = 176.36 } #MC54: C5H5 + CH3 -> C-C6H8 { A = 6.25E+48 n =-10.44 E = 80.04 } # Reactions of C6H7 MC55: C-C6H7 -> N-C4H5 + C2H2 { A = 2.51E+14 n = 0.70 E = 175.00 } MC56: C-C6H7 -> A1-C6H6 + H { A = 6.66E+11 n = -0.59 E = 66.19 } # Reactions of C5H9 MC57: AD-C5H9 -> T-C3H5 + C2H4 { A = 6.15E+12 n = 0.29 E = 170.08 } MC58: AD-C5H9 -> C2H3 + C3H6 { A = 3.68E+23 n = -2.99 E = 186.10 } MC59: AD-C5H9 -> CH3 + C4H6 { A = 1.03E+09 n = 0.88 E = 147.55 } MC60: AD-C5H9 -> H + I-C5H8 { A = 6.42e+10 n = 0.45 E = 135.37 } MC61: C5H9 -> C4H6 + CH3 { A = 1.34E+15 n = -0.52 E = 160.33 } MC62: C5H9 -> C3H6 + C2H3 { A = 5.20E+14 n = 0.19 E = 216.80 } MC63: C5H9 -> C5H8 + H { A = 1.78E+14 n = 0.07 E = 183.27 } MC64: C5H9 -> A-C3H5 + C2H4 { A = 2.50E+13 n = .00 E = 188.28 } MC65: C5H9 -> S-C3H5 + C2H4 { A = 8.73E+13 n = 0.41 E = 229.96 } MC66: C5H9 + HO2 -> C5H8 + H2O2 { A = 2.00E+12 n = .00 E = .00 } MC67: C5H9 + CH3 -> C5H8 + CH4 { A = 2.00E+12 n = .00 E = .00 } MC68: C5H9 + CH3O2 -> C5H8 + CH3O + OH { A = 2.00E+12 n = .00 E = .00 } # Reactions of C5H8 MC69f: I-C5H7 + H -> I-C5H8 { A = 1.99E+14 n = .00 E = .00 } MC70: I-C5H8 + H -> I-C5H7 + H2 { A = 1.73E+05 n = 2.50 E = 10.43 } MC71: I-C5H8 + O -> I-C5H7 + OH { A = 4.41E+05 n = 2.42 E = 13.18 } MC72: I-C5H8 + OH -> I-C5H7 + H2O { A = 3.12E+06 n = 2.00 E = -1.25 } MC73: I-C5H8 + CH3 -> I-C5H7 + CH4 { A = 2.21E+00 n = 3.50 E = 23.74 } MC74: I-C5H8 + HO2 -> I-C5H7 + H2O2 { A = 9.64E+03 n = 2.60 E = 58.20 } MC75: C5H8 -> H + C5H7 { A = 1.04E+21 n = -1.35 E = 357.34 } MC76: C5H7 + H -> C5H8 { A = 3.23E+20 n = -1.67 E = 14.03 } MC77: C5H8 + H -> C4H6 + CH3 { A = 5.20E+71 n =-16.38 E = 213.64 } MC78: C5H8 + H -> C5H7 + H2 { A = 2.13E+06 n = 2.28 E = -8.79 } MC79: C5H8 + O -> C5H7 + OH { A = 5.24E+11 n = 0.70 E = 24.62 } MC80: C5H8 + OH -> C5H7 + H2O { A = 3.12E+06 n = 2.00 E = -1.25 } MC81: C5H8 + CH3 -> C5H7 + CH4 { A = 2.21E+00 n = 3.50 E = 23.74 } MC82: C5H8 + HO2 -> C5H7 + H2O2 { A = 1.50E+11 n = .00 E = 59.37 } # Reactions of C5H7 MC83: I-C5H7 -> A-C3H4 + C2H3 { A = 2.48E+15 n = -0.23 E = 293.33 } MC84: I-C5H7 + HO2 -> N-C4H5 + CH2O + OH { A = 7.00E+12 n = .00 E = -4.18 } MC85: J-C5H7 + O2 -> C2H3CHO + CH2CHO { A = 1.23E+36 n = -7.25 E = 140.58 } MC86f: J-C5H7 -> C5H7 { A = 5.35E+11 n = -0.70 E = 0.25 } MC87f: C5H6 + H -> J-C5H7 { A = 4.80E+12 n = -0.18 E = 13.18 } #Redcued MC88: C5H7 + O2 -> A-C3H5 + CH2O + CO { A = 8.16E+10 n = 0.18 E = 38.24 } MC89f: C5H7 + H -> N-C4H5 + CH3 { A = 2.91E+26 n = -2.18 E = 153.85 } /* MC85: C5H7 + O2 -> C2H3CHO + CH2CHO { A = 7.60E+34 n = -7.10 E = 136.98 } MC86: C5H7 + O2 -> A-C3H5 + CO + CH2O { A = 1.13E+11 n = 0.11 E = 39.64 } MC87: C5H6 + H -> C5H7 { A = 1.40E+14 n = -0.18 E = 13.18 } MC88: C5H7 -> H + C5H6 { A = 4.46E+12 n = -0.29 E = 150.73 } MC89: C5H7 + H -> N-C4H5 + CH3 { A = 4.03E+26 n = -2.25 E = 155.24 } MC90: N-C4H5 + CH3 -> C5H7 + H { A = 5.98E+19 n = -0.79 E = 74.89 } */ /* MC99: MCHR-C7H13 + O2 -> MCHE-C7H12 + HO2 { A = 3.26E+11 n = 0.16 E = 32.04 } MC98: MCHR-C7H13 + O2 -> MCH1OO-C7H13O2 { A = 1.50E+03 n = 2.61 E = -24.58 } MC97: MCHE-C7H12 + HO2 -> MCH2QJ1-C7H13O2 { A = 1.20E+11 n = 0.03 E = 26.42 } MC96: MCH2QJ1-C7H13O2 -> HO2 + MCHE-C7H12 { A = 1.11E+49 n = 10.11 E = 201.73 } */ #==========================================================================# # # # PAH chemistry # # HACA Based Mechanism # # # #==========================================================================# # ----------------- # # Fulvene - C5H4CH2 # # ----------------- # # Marinov 1998 (x0.5) P000f: C5H4CH2 + H -> A1-C6H6 + H { A = 1.50E+12 n = 0.50 E = 8.37 } # Senosiain & Miller 2007 (JPCA) # P=1bar P001f: N-C4H5 + C2H2 -> C5H4CH2 + H { A = 4.62E+15 n = -0.89 E = 38.25 } P002f: I-C4H5 + C2H2 -> C5H4CH2 + H { A = 6.80E+24 n = -3.45 E = 85.09 } # P=10bar #001f: N-C4H5 + C2H2 -> C5H4CH2 + H { A = 1.74E+19 n = -1.86 E = 51.81 } #002f: I-C4H5 + C2H2 -> C5H4CH2 + H { A = 9.69E+25 n = -3.76 E = 89.23 } # Miller & Klippenstein 2003 # P=1bar P003f: C5H4CH2 -> A1-C6H6 { A = 1.45E+45 n = -8.90 E = 405.86 } P004f: C5H4CH2 -> A1--C6H5 + H { A = 2.24E+68 n =-14.65 E = 596.54 } # P=10bar #003f: C5H4CH2 -> A1-C6H6 { A = 2.95E+31 n = -4.97 E = 370.14 } #004f: C5H4CH2 -> A1--C6H5 + H { A = 8.51E+24 n = -2.51 E = 474.17 } # ------------ # # Benzene - A1 # # ------------ # # Wang & Frenklach 1997 P005f: N-C4H3 + C2H2 -> A1--C6H5 { A = 9.60E+70 n =-17.77 E = 130.96 } # Senosiain & Miller 2007 (JPCA) # P=1bar P006f: N-C4H5 + C2H2 -> A1-C6H6 + H { A = 1.38E+16 n = -1.00 E = 37.24 } P007f: I-C4H5 + C2H2 -> A1-C6H6 + H { A = 1.67E+23 n = -3.30 E = 104.43 } # P=10bar #006f: N-C4H5 + C2H2 -> A1-C6H6 + H { A = 1.69E+16 n = -1.03 E = 37.52 } #007f: I-C4H5 + C2H2 -> A1-C6H6 + H { A = 8.25E+24 n = -3.76 E = 111.14 } # Miller, Klippenstein, Georgievskii, Harding, Allen, Simmonett 2010 # P=1bar - Fitted rate valid for 600K-2500K P008 : A-C3H5 + C3H3 -> C5H4CH2 + 2H { A = 1.88E+38 n = -7.53 E = 99.91 } # Georgievskii, Miller, & Klippenstein 2007 # -> Total rate at 1bar # Miller & Klippenstein 2003 # -> Branching ratios # -> 2-ethynyl-1,3-butadiene lumped into Fulvene # Fitted rates valid for 800K-2000K # P=1bar P009f: C3H3 + C3H3 -> C5H4CH2 { A = 8.25E+46 n =-10.10 E = 70.96 } P010f: C3H3 + C3H3 -> A1-C6H6 { A = 1.07E+45 n = -9.57 E = 71.19 } P011f: C3H3 + C3H3 -> A1--C6H5 + H { A = 5.77E+37 n = -7.00 E = 131.82 } # P=10bar #009f: C3H3 + C3H3 -> C5H4CH2 { A = 5.53E+42 n = -8.77 E = 66.38 } #010f: C3H3 + C3H3 -> A1-C6H6 { A = 7.17E+40 n = -8.24 E = 66.61 } #011f: C3H3 + C3H3 -> A1--C6H5 + H { A = 3.87E+33 n = -5.67 E = 127.24 } # Tokmakov & Lin 2004 P015f: A1--C6H5 + C2H4 -> A1-C6H6 + C2H3 { A = 9.45E-03 n = 4.47 E = 18.71 } # ---------------- # # Naphthalene - A2 # # ---------------- # # Kislov & Mebel 2005 K100f: A1C2H*-C8H5 + C2H2 -> A2--C10H7 { A = 1.34E+04 n = 2.50 E = 5.37 } K102f: A1C2H3*-C8H7 + C2H2 -> A2-C10H8 + H { A = 3.02E+03 n = 2.55 E = 13.31 } # Senosiain & Miller 2007 (JPCA) # From n-C4H5+C2H2 (HPL) # Total addition rate independent of pressure => use HPL P104f: A1C2H2-C8H7 + C2H2 -> A2-C10H8 + H { A = 3.80E+07 n = 1.62 E = 18.57 } # From A1 (x1/3) P105f: A1C2H-C8H6 + C2H3 -> A2-C10H8 + H { A = 3.60E+17 n = -1.44 E = 65.93 } # From A1- P106f: A1C2H*-C8H5 + C2H4 -> A2-C10H8 + H { A = 3.62E+28 n = -4.24 E = 99.85 } # Aguilera-Iparraguirre & Klopper 2007 # Total entrance channel rate P107f: A1--C6H5 + C4H4 -> A2-C10H8 + H { A = 1.26E+04 n = 2.61 E = 6.00 } # From A1 (x2/3) P108f: A2-C10H8 -> A2--C10H7 + H { A = 8.60E+60 n =-12.48 E = 619.55 } K109f: A2-C10H8 + H -> A2--C10H7 + H2 { A = 2.65E+08 n = 1.87 E = 71.53 } K110f: A2-C10H8 + OH -> A2--C10H7 + H2O { A = 9.63E+02 n = 3.02 E = 18.30 } # From A1 (x2/3) P111f: A2-C10H8 -> A2*-C10H7 + H { A = 8.60E+60 n =-12.48 E = 619.55 } K112f: A2-C10H8 + H -> A2*-C10H7 + H2 { A = 2.65E+08 n = 1.87 E = 71.53 } K113f: A2-C10H8 + OH -> A2*-C10H7 + H2O { A = 9.63E+02 n = 3.02 E = 18.30 } # Park, Nguyen, Xu, Lin 2009 P113f: A2--C10H7 -> A2*-C10H7 { A = 1.51E+07 n = .00 E = 184.85 } P114f: A2--C10H7 + C2H2 -> A2C2H2A-C12H9 { A = 2.81E+07 n = 1.77 E = 9.37 } P115f: A2*-C10H7 + C2H2 -> A2C2H2B-C12H9 { A = 5.38E+07 n = 1.65 E = 10.71 } # From A1- P116f: A2--C10H7 + C2H3 -> A2C2H2A-C12H9 + H { A = 6.00E+12 n = .00 E = .00 } P117f: A2*-C10H7 + C2H3 -> A2C2H2B-C12H9 + H { A = 6.00E+12 n = .00 E = .00 } # From A1 (x2/3) P118f: A2-C10H8 + C2H3 -> A2C2H2A-C12H9 + H2 { A = 7.20E+17 n = -1.44 E = 65.93 } P119f: A2-C10H8 + C2H3 -> A2C2H2B-C12H9 + H2 { A = 7.20E+17 n = -1.44 E = 65.93 } # From A1- P120f: A2--C10H7 + C2H4 -> A2C2H2A-C12H9 + H2 { A = 3.62E+28 n = -4.24 E = 99.85 } P121f: A2*-C10H7 + C2H4 -> A2C2H2B-C12H9 + H2 { A = 3.62E+28 n = -4.24 E = 99.85 } # From A1C2H2 K122f: A2C2H2A-C12H9 -> A2C2HA-C12H8 + H { A = 7.18E+10 n = 1.02 E = 161.81 } K123f: A2C2H2A-C12H9 + H -> A2C2HA-C12H8 + H2 { A = 1.65E+11 n = 0.49 E = 44.48 } P124f: A2C2H2A-C12H9 + OH -> A2C2HA-C12H8 + H2O { A = 2.50E+12 n = .00 E = .00 } K125f: A2C2H2B-C12H9 -> A2C2HB-C12H8 + H { A = 7.18E+10 n = 1.02 E = 161.81 } K126f: A2C2H2B-C12H9 + H -> A2C2HB-C12H8 + H2 { A = 1.65E+11 n = 0.49 E = 44.48 } P127f: A2C2H2B-C12H9 + OH -> A2C2HB-C12H8 + H2O { A = 2.50E+12 n = .00 E = .00 } # From A1 (x1/6) P128f: A2C2HA-C12H8 -> A2C2HA*-C12H7 + H { A = 2.15E+60 n =-12.48 E = 619.55 } K129f: A2C2HA-C12H8 + H -> A2C2HA*-C12H7 + H2 { A = 1.32E+08 n = 1.88 E = 70.38 } P130f: A2C2HA-C12H8 + OH -> A2C2HA*-C12H7 + H2O { A = 6.72E+01 n = 3.33 E = 6.09 } P131f: A2C2HB-C12H8 -> A2C2HB*-C12H7 + H { A = 2.15E+60 n =-12.48 E = 619.55 } K132f: A2C2HB-C12H8 + H -> A2C2HB*-C12H7 + H2 { A = 1.32E+08 n = 1.88 E = 70.38 } P133f: A2C2HB-C12H8 + OH -> A2C2HB*-C12H7 + H2O { A = 6.72E+01 n = 3.33 E = 6.09 } # --------------------- # # Acenaphthalene - A2R5 # # --------------------- # # Kislov & Mebel 2005 K200f: A2C2H2A-C12H9 -> A2R5-C12H8 + H { A = 2.88E+11 n = 0.23 E = 71.24 } # Lifshitz, Tambura & Dubnikova 2007 P201f: A2C2HA-C12H8 + H -> A2R5-C12H8 + H { A = 3.52E+12 n = .00 E = 55.90 } # From A1 (x2/3) P202f: A2R5-C12H8 -> A2R5--C12H7 + H { A = 8.60E+60 n =-12.48 E = 619.55 } K203f: A2R5-C12H8 + H -> A2R5--C12H7 + H2 { A = 2.65E+08 n = 1.87 E = 71.53 } K204f: A2R5-C12H8 + OH -> A2R5--C12H7 + H2O { A = 9.63E+02 n = 3.02 E = 18.30 } # From A1- K205f: A2R5--C12H7 + C2H2 -> A2R5C2H2-C14H9 { A = 3.29E+06 n = 2.05 E = 13.23 } # From A1- P206f: A2R5--C12H7 + C2H3 -> A2R5C2H2-C14H9 + H { A = 6.00E+12 n = .00 E = .00 } # From A1 (x2/3) P207f: A2R5-C12H8 + C2H3 -> A2R5C2H2-C14H9 + H2 { A = 3.60E+17 n = -1.44 E = 65.93 } # From A1- P208f: A2R5--C12H7 + C2H4 -> A2R5C2H2-C14H9 + H2 { A = 3.62E+28 n = -4.24 E = 99.85 } # From A1 (x1/6) P209f: A2R5C2H-C14H8 -> A2R5C2H*-C14H7 + H { A = 2.15E+60 n =-12.48 E = 619.55 } K210f: A2R5C2H-C14H8 + H -> A2R5C2H*-C14H7 + H2 { A = 1.32E+08 n = 1.88 E = 70.38 } P211f: A2R5C2H-C14H8 + OH -> A2R5C2H*-C14H7 + H2O { A = 6.72E+01 n = 3.33 E = 6.09 } # From A1C2H2 K212f: A2R5C2H2-C14H9 -> A2R5C2H-C14H8 + H { A = 7.18E+10 n = 1.02 E = 161.81 } K213f: A2R5C2H2-C14H9 + H -> A2R5C2H-C14H8 + H2 { A = 1.65E+11 n = 0.49 E = 44.48 } P214f: A2R5C2H2-C14H9 + OH -> A2R5C2H-C14H8 + H2O { A = 2.50E+12 n = .00 E = .00 } # ------------- # # Biphenyl - P2 # # ------------- # # Park, Burova,, Rodgers & Lin 1999 # Fitted exp rate P301f: A1-C6H6 + A1--C6H5 -> P2-C12H10 + H { A = 9.55E+11 n = .00 E = 9.07 } # Tranter, Klippenstein, Harding, Giri, Yang, Keifer 2010 P302f: A1--C6H5 + A1--C6H5 -> P2-C12H10 { A = 7.34E+20 n = -2.34 E = 17.26 } P303f: A1--C6H5 + A1--C6H5 -> P2--C12H9 + H { A = 2.44E+13 n = 0.89 E = 180.66 } # From A1 (x2/3) P304f: P2-C12H10 -> P2--C12H9 + H { A = 8.60E+60 n =-12.48 E = 619.55 } P305f: P2-C12H10 + H -> P2--C12H9 + H2 { A = 4.01E+08 n = 1.80 E = 68.42 } P306f: P2-C12H10 + OH -> P2--C12H9 + H2O { A = 2.69E+02 n = 3.33 E = 6.09 } # ----------------- # # Phenanthrene - A3 # # ----------------- # # Kislov & Mebel 2005 # Same as for A1C2H* K401f: A2C2HA*-C12H7 + C2H2 -> A3--C14H9 { A = 1.34E+04 n = 2.50 E = 5.37 } K403f: A2C2HB*-C12H7 + C2H2 -> A3--C14H9 { A = 1.34E+04 n = 2.50 E = 5.37 } # Senosiain & Miller 2007 (JPCA) # From n-C4H5+C2H2 (HPL) P405f: A2C2H2A-C12H9 + C2H2 -> A3-C14H10 + H { A = 3.80E+07 n = 1.62 E = 18.57 } P406f: A2C2H2B-C12H9 + C2H2 -> A3-C14H10 + H { A = 3.80E+07 n = 1.62 E = 18.57 } # From A1- P407f: P2--C12H9 + C2H2 -> A3-C14H10 + H { A = 3.29E+06 n = 2.05 E = 13.23 } # From A1- P408f: A2C2HA*-C12H7 + C2H3 -> A3-C14H10 { A = 6.00E+12 n = .00 E = .00 } P409f: A2C2HB*-C12H7 + C2H3 -> A3-C14H10 { A = 6.00E+12 n = .00 E = .00 } # From A1 (x1/6) P410f: A2C2HA-C12H8 + C2H3 -> A3-C14H10 + H { A = 1.80E+17 n = -1.44 E = 65.93 } P411f: A2C2HB-C12H8 + C2H3 -> A3-C14H10 + H { A = 1.80E+17 n = -1.44 E = 65.93 } # From A1- P412f: A2C2HA*-C12H7 + C2H4 -> A3-C14H10 + H { A = 3.62E+28 n = -4.24 E = 99.85 } P413f: A2C2HB*-C12H7 + C2H4 -> A3-C14H10 + H { A = 3.62E+28 n = -4.24 E = 99.85 } # From A1- P414f: A2--C10H7 + C4H4 -> A3-C14H10 + H { A = 1.26E+04 n = 2.61 E = 6.00 } P415f: A2*-C10H7 + C4H4 -> A3-C14H10 + H { A = 1.26E+04 n = 2.61 E = 6.00 } # From P2 (x1/3) P416f: A1C2H-C8H6 + A1--C6H5 -> A3-C14H10 + H { A = 3.18E+11 n = .00 E = 9.07 } # From P2 & P2- # Reduced (x1/4) because of C2H group P417f: A1C2H*-C8H5 + A1-C6H6 -> A3-C14H10 + H { A = 2.39E+11 n = .00 E = 9.07 } # From P2 & P2- P418f: A1C2H*-C8H5 + A1--C6H5 -> A3-C14H10 { A = 1.39E+13 n = .00 E = 0.47 } # From A1 (x1/3) P419f: A3-C14H10 -> A3--C14H9 + H { A = 4.30E+60 n =-12.48 E = 619.55 } K420f: A3-C14H10 + H -> A3--C14H9 + H2 { A = 2.00E+08 n = 1.80 E = 68.42 } K421f: A3-C14H10 + OH -> A3--C14H9 + H2O { A = 1.34E+02 n = 3.33 E = 6.09 } # From A1 (x2/3) & A2 P422f: A3-C14H10 -> A3*-C14H9 + H { A = 4.30E+60 n =-12.48 E = 619.55 } K423f: A3-C14H10 + H -> A3*-C14H9 + H2 { A = 2.65E+08 n = 1.87 E = 71.53 } K424f: A3-C14H10 + OH -> A3*-C14H9 + H2O { A = 9.63E+02 n = 3.02 E = 18.30 } # Frenklach 2005 P425f: A3--C14H9 -> A2R5--C12H7 + C2H2 { A = 1.30E+11 n = 1.08 E = 294.55 } # ------------------------ # # Acephenanthrylene - A3R5 # # ------------------------ # # Kislov & Mebel 2005 # Same as for A1C2H* P501f: A2R5C2H*-C14H7 + C2H2 -> A3R5--C16H9 { A = 1.34E+04 n = 2.50 E = 5.37 } # Senosiain & Miller 2007 (JPCA) # From n-C4H5+C2H2 (HPL) P502f: A2R5C2H2-C14H9 + C2H2 -> A3R5-C16H10 + H { A = 3.80E+07 n = 1.62 E = 18.57 } # From A2- P503f: A3*-C14H9 + C2H2 -> A3R5-C16H10 + H { A = 1.28E+06 n = 2.05 E = 8.08 } # From A1- P504f: A3*-C14H9 + C2H3 -> A3R5-C16H10 + H2 { A = 6.00E+12 n = .00 E = .00 } # From A1- P505f: A2R5--C12H7 + C4H4 -> A3R5-C16H10 + H { A = 1.26E+04 n = 2.61 E = 6.00 } # From A1 (x1/6) P506f: A3R5-C16H10 -> A3R5--C16H9 + H { A = 2.15E+60 n =-12.48 E = 619.55 } K507f: A3R5-C16H10 + H -> A3R5--C16H9 + H2 { A = 2.65E+08 n = 1.87 E = 71.53 } K508f: A3R5-C16H10 + OH -> A3R5--C16H9 + H2O { A = 9.63E+02 n = 3.02 E = 18.30 } # ----------- # # Pyrene - A4 # # ----------- # # From A2- K600f: A3--C14H9 + C2H2 -> A4-C16H10 + H { A = 1.28E+06 n = 2.05 E = 8.08 } # From A2 (x2) P601f: A4-C16H10 -> A4--C16H9 + H { A = 1.72E+60 n =-12.48 E = 619.55 } K602f: A4-C16H10 + H -> A4--C16H9 + H2 { A = 5.30E+08 n = 1.87 E = 71.53 } K603f: A4-C16H10 + OH -> A4--C16H9 + H2O { A = 1.93E+03 n = 3.02 E = 18.30 } # --------------------------- # # Cyclopenta[cd]pyrene - A4R5 # # --------------------------- # # From A2- K700f: A4--C16H9 + C2H2 -> A4R5-C18H10 + H { A = 1.28E+06 n = 2.05 E = 8.08 } K701f: A3R5--C16H9 + C2H2 -> A4R5-C18H10 + H { A = 1.28E+06 n = 2.05 E = 8.08 } # ------------------- # # Fluoranthene - FLTN # # ------------------- # # From A1+A1- (x2/3 and x1) P800 : A2-C10H8 + A1--C6H5 -> FLTN-C16H10 + H + H2 { A = 6.37E+11 n = .00 E = 9.07 } P801 : A2--C10H7 + A1-C6H6 -> FLTN-C16H10 + H + H2 { A = 9.55E+11 n = .00 E = 9.07 } # From A1-+A1- P802 : A2--C10H7 + A1--C6H5 -> FLTN-C16H10 + H2 { A = 1.39E+13 n = .00 E = 0.47 } #==========================================================================# # # # Cyclopentadiene chemistry # # # # Zhong & Bozzelli, Int. J. Chem. Kinet., 1997, 29, 893-913 # # Zhong & Bozzelli, J. Phys. Chem. A, 1998, 102, 3537-3555 # # # #==========================================================================# # Cyclopentadiene # --------------- # Tokmakov, Moskaleva & Lin 2003 # Rate at 2bar CP01f: C5H6 -> C5H5 + H { A = 1.73E+68 n =-15.16 E = 486.90 } # Roy's Thesis 1999 # 1/2 of each C3H5 CP02f: C5H6 + H -> C5H5 + H2 { A = 2.80E+13 n = .00 E = 9.45 } CP03f: C5H6 + H -> A-C3H5 + C2H2 { A = 3.30E+14 n = .00 E = 51.65 } CP04 : C5H6 + H -> S-C3H5 + C2H2 { A = 3.30E+14 n = .00 E = 51.65 } CP05f: C5H6 + O -> C5H5 + OH { A = 4.77E+04 n = 2.71 E = 4.63 } CP06f: C5H6 + OH -> C5H5 + H2O { A = 3.08E+06 n = 2.00 E = .00 } CP07f: C5H6 + O2 -> C5H5 + HO2 { A = 1.00E+14 n = .00 E = 155.44 } CP08f: C5H6 + HO2 -> C5H5 + H2O2 { A = 1.10E+04 n = 2.60 E = 53.97 } CP09f: C5H6 + CH3 -> C5H5 + CH4 { A = 1.80E-01 n = 4.00 E = .00 } # Burcat, Dvianyaninov, & Olchanski 2001 CP10f: C5H6 + C2H3 -> C5H5 + C2H4 { A = 6.00E+12 n = .00 E = .00 } CP11f: C5H6 + N-C4H5 -> C5H5 + C4H6 { A = 6.00E+12 n = .00 E = .00 } # From C2H4 + O CP12f: C5H6 + O -> T-C5H5O + H { A = 7.66E+09 n = 0.88 E = 4.77 } CP13 : C5H6 + O -> C2H4 + C2H2 + CO { A = 3.89E+08 n = 1.36 E = 3.71 } # From C2H4 + OH CP14 : C5H6 + OH -> C4H6 + HCO { A = 3.75E+36 n = -7.80 E = 29.54 } CP15 : C5H6 + OH -> C2H4 + C2H2 + HCO { A = 3.75E+36 n = -7.80 E = 29.54 } # Cyclopentadienyl radical # ------------------------ # Moskaleva & Lin 2000 # Knyazev & Slagle 2002 CP16f: C3H3 + C2H2 -> C5H5 { A = 6.87E+55 n =-12.50 E = 176.00 } # Murakami et al. 2003 - Total rate # Kislov & Mebel - Branching ratio CP17 : C5H5 + C5H5 -> A2-C10H8 + 2 H { A = 6.39E+29 n = -4.03 E = 147.30 } # Melius, Colvin, Marinov, Pitz, & Senkan 1996 # Sharma & Green 2009 - Rate fillted at P=1bar CP18 : C5H5 + CH3 -> C5H4CH2 + 2 H { A = 4.91E+31 n = -4.85 E = 103.65 } # Frank, Herzler, Just & Wahl 1994 CP19f: C5H5 + O -> C5H4O + H { A = 7.00E+13 n = .00 E = .00 } # From A-C3H5 + O2 # Lee & Bozzelli 2005 - Total rate CP20f: C5H5 + O2 -> C5H4O + OH { A = 4.34E+07 n = 1.30 E = 73.92 } # From C2H5+HO2 CP21f: C5H5 + HO2 -> S-C5H5O + OH { A = 3.10E+13 n = .00 E = .00 } # Zhong & Bozzelli 1998 # Entrance rate x2.0 CP22 : C5H5 + OH -> S-C5H5O + H { A = 1.02E+13 n = .00 E = .00 } # Cyclopentadienoxy radical # ------------------------- CP23f: S-C5H5O -> C5H4O + H { A = 2.00E+13 n = .00 E = 125.52 } CP24 : T-C5H5O -> N-C4H5 + CO { A = 1.00E+12 n = .00 E = 150.62 } # 1/3 rate from CH3O CP25 : S-C5H5O + H -> C5H4O + H2 { A = 6.67E+12 n = .00 E = .00 } CP26 : S-C5H5O + O -> C5H4O + OH { A = 3.33E+12 n = .00 E = .00 } CP27 : S-C5H5O + OH -> C5H4O + H2O { A = 1.67E+12 n = .00 E = .00 } CP28 : S-C5H5O + O2 -> C5H4O + HO2 { A = 1.43E-13 n = 7.60 E = -14.77 } # 2/3 rate from C2H5 CP29 : T-C5H5O + H -> C5H4O + H2 { A = 1.33E+12 n = .00 E = .00 } CP30 : T-C5H5O + O2 -> C5H4O + HO2 { A = 1.28E+07 n = 1.02 E = -8.51 } # Cyclopentadienone # ----------------- # Wang & Brezinsky 1998 # Fitted CP31 : C5H4O -> 2 C2H2 + CO { A = 3.37E+44 n = -8.00 E = 454.70 } # HPL From C2H4+H CP32f: C5H4O + H -> T-C5H5O { A = 2.74E+09 n = 1.46 E = 5.67 } CP33f: C5H4O + O -> C4H4 + CO2 { A = 1.00E+13 n = .00 E = 8.37 } # Kislov & Mebel 2008 - Full entrance rate CP34 : C5H5 + C5H6 -> C9H8 + CH3 { A = 7.86E-01 n = 3.07 E = 23.97 } #==========================================================================# # # # Indene chemistry # # Adapted from Cyclopentadiene # # # #==========================================================================# # Indene # ------ # Kislov & Mebel 2007 # Rate estimated I00f: A1--C6H5 + C3H3 -> C9H8 { A = 1.00E+13 n = .00 E = .00 } # Same rate as for C5H6 I01f: C9H8 -> C9H7 + H { A = 1.73E+68 n =-15.16 E = 486.90 } # Same rate as for C5H6 I02f: C9H8 + H -> C9H7 + H2 { A = 2.80E+13 n = .00 E = 9.45 } # Kislov & Mebel 2007 I03f: A1CH2-C7H7 + C2H2 -> C9H8 + H { A = 3.16E+04 n = 2.48 E = 46.28 } # TEST - GB #I41f: C9H8 + H -> A1-C6H6 + C3H3 { A = 3.30E+13 n = .00 E = 51.65 } #I42f: C9H8 + H -> A1C2H-C8H6 + CH3 { A = 3.30E+13 n = .00 E = 51.65 } # Same rate as for C5H6 I05f: C9H8 + O -> C9H7 + OH { A = 4.77E+04 n = 2.71 E = 4.63 } I06f: C9H8 + OH -> C9H7 + H2O { A = 3.08E+06 n = 2.00 E = .00 } I07f: C9H8 + O2 -> C9H7 + HO2 { A = 1.00E+14 n = .00 E = 155.44 } I08f: C9H8 + HO2 -> C9H7 + H2O2 { A = 1.10E+04 n = 2.60 E = 53.97 } I09f: C9H8 + CH3 -> C9H7 + CH4 { A = 1.80E-01 n = 4.00 E = .00 } # From C2H4 + O I12 : C9H8 + O -> O-C6H4 + C2H3 + CO + H { A = 1.02E+08 n = 1.66 E = 2.75 } # From C2H4 + OH I15 : C9H8 + OH -> A1C2H3-C8H8 + HCO { A = 1.88E+36 n = -7.80 E = 29.54 } # Indenyl radical # 2/5 of the rate for C5H5 # ------------------------ I17 : C9H7 + C5H5 -> A3-C14H10 + 2H { A = 2.56E+29 n = -4.03 E = 147.30 } I18 : C9H7 + CH3 -> A2-C10H8 + 2H { A = 1.96E+31 n = -4.85 E = 103.65 } # TEST - GB #I40 : C9H7 -> C5H5 + C4H2 { A = 1.00E+10 n= .00 E = 250.00 } I19f: C9H7 + O -> C9H6O + H { A = 2.80E+13 n = .00 E = .00 } I20f: C9H7 + O2 -> C9H6O + OH { A = 1.74E+07 n = 1.30 E = 73.92 } I21 : C9H7 + HO2 -> C9H6O + H2O { A = 1.24E+13 n = .00 E = .00 } I22 : C9H7 + OH -> C9H6O + 2H { A = 4.08E+12 n = .00 E = .00 } # From A-C3H5 + C3H3 I23 : C9H7 + C3H3 -> A2R5-C12H8 + 2H { A = 1.88E+38 n = -7.53 E = 99.91 } # Indenone # -------- # Wang & Brezinsky 1998 I31 : C9H6O -> O-C6H4 + C2H2 + CO { A = 3.37E+44 n = -8.00 E = 454.70 } # From C5H4O+H I32 : C9H6O + H -> A1C2H3*-C8H7 + CO { A = 1.37E+09 n = 1.46 E = 5.67 } #==========================================================================# # # # Toluene chemistry # # # # "Investigation of the reaction of toluene with molecular oxygen # # in shock-heated gases" # # Oehlschlaeger, Davidson & Hanson 2006 # # Combust. Flame 147 (2006) 195-208 # # # #==========================================================================# # Toluene / Benzyl decomposition # ------------------------------ # Tokmakov et al. 2001 (x1.2 to match exp.) T01f: A1CH3-C7H8 + H -> A1-C6H6 + CH3 { A = 2.31E+06 n = 2.17 E = 17.42 } # Klippenstein et al. 2007 # Almost indep or pressure => HPL T02f: A1CH3-C7H8 -> A1CH2-C7H7 + H { A = 1.56E+13 n = 0.68 E = 373.24 } T03f: A1CH3-C7H8 -> A1--C6H5 + CH3 { A = 4.35E+22 n = -1.73 E = 436.01 } # P=1bar - 1000K-2500K T04f: A1CH2-C7H7 + H -> A1--C6H5 + CH3 { A = 5.83E+67 n =-14.15 E = 285.89 } # P=10bar - 1200K-2500K #04f: A1CH2-C7H7 + H -> A1--C6H5 + CH3 { A = 8.85E+68 n =-14.23 E = 328.07 } # Assumed products. Other choices: C7H6 + H, c-C7H7 # Rate from Oehlschlaeger et al. 2006 (1.5 atm) (25%) T05f: A1CH2-C7H7 -> C5H5 + C2H2 { A = 8.20E+14 n = .00 E = 337.55 } # Toluene # ------- # Oehlschlaeger et al. 2006 (1.5 atm) (20%) T06f: A1CH3-C7H8 + O2 -> A1CH2-C7H7 + HO2 { A = 2.18E+07 n = 2.50 E = 192.65 } # Oehlschlaeger et al. 2006 (1.5 atm) (25%) T07f: A1CH3-C7H8 + H -> A1CH2-C7H7 + H2 { A = 6.47E+00 n = 3.98 E = 14.16 } # Seta, Nakajima & Miyoshi 2006 (35%) # Better match with Vasudevan, Davidson & Hanson 2005 T08f: A1CH3-C7H8 + OH -> A1CH2-C7H7 + H2O { A = 1.77E+05 n = 2.39 E = -2.52 } T09f: A1CH3-C7H8 + OH -> A1OH-C6H6O + CH3 { A = 7.83E+02 n = 2.88 E = 13.48 } T10f: A1CH3-C7H8 + OH -> HOA1CH3-C7H8O + H { A = 3.14E+01 n = 3.37 E = 19.75 } # From C3H8+O (x0.5) T11f: A1CH3-C7H8 + O -> A1CH2-C7H7 + OH { A = 1.18E+00 n = 4.09 E = 10.65 } # From A1+O (x5/6) T12f: A1CH3-C7H8 + O -> HOA1CH3-C7H8O { A = 1.69E+12 n = 0.30 E = 18.42 } T13f: A1CH3-C7H8 + O -> OA1CH3-C7H7O + H { A = 1.66E+07 n = 1.80 E = 16.63 } # From C2H6+R (x0.5) T14f: A1CH3-C7H8 + CH3 -> A1CH2-C7H7 + CH4 { A = 4.22E+14 n = .00 E = 93.12 } # Baulch et al. 2005 T15f: A1CH3-C7H8 + HO2 -> A1CH2-C7H7 + H2O2 { A = 9.33E+04 n = 2.50 E = 61.44 } # Heckmann, Hippler & Troe 1996 T16f: A1CH3-C7H8 + A1--C6H5 -> A1CH2-C7H7 + A1-C6H6 { A = 7.94E+13 n = .00 E = 50.00 } # Benzyl radical # -------------- # Baulch et al. 2005 - k=3.3e14 # Reduced to collision limit rate at T=298K T17f: A1CH2-C7H7 + O -> A1CH2O-C7H7O { A = 2.28E+14 n = .00 E = .00 } # Hippler, Reihs & Troe 1991 T18f: A1CH2-C7H7 + OH -> A1CH2OH-C7H8O { A = 2.00E+13 n = .00 E = .00 } # da Silva & Bozzelli 2008 T19f: A1CH2-C7H7 + HO2 -> A1CH2O-C7H7O + OH { A = 1.19E+09 n = 1.03 E = -9.41 } # From A-C3H5 + C3H3 T20 : A1CH2-C7H7 + C3H3 -> A2-C10H8 + 2H { A = 1.88E+38 n = -7.53 E = 99.91 } # Murakami et al. 2007 - HPL # Canneaux et al. 2008 - Benzylperoxy isomerization # Benzylperoxy in Steady State T21f: A1CH2-C7H7 + O2 -> A1CHO-C7H6O + OH { A = 3.76E+15 n = -1.55 E = 47.37 } # From A-C3H5 + O2 T22f: A1CH2-C7H7 + O2 -> A1O-C6H5O + CH2O { A = 6.26E+37 n = -8.86 E = 69.38 } # Benzyl Alcohol / Alcoxy Benzyl # ------------------------------ # From CH3OH+R->CH3O+RH T23f: A1CH2O-C7H7O + H + M9 -> A1CH2OH-C7H8O + M9 { A = 4.66E+41 n = -7.44 E = 58.91 Ai= 2.43E+12 ni= .52 Ei= 0.21 fcA = 0.30 fctA = 100 fcb = 0.70 fctb = 90000 fcc = 1.0 fctc = 10000 } T24f: A1CH2OH-C7H8O + H -> A1CH2O-C7H7O + H2 { A = 4.20E+06 n = 2.10 E = 20.38 } T25f: A1CH2OH-C7H8O + O -> A1CH2O-C7H7O + OH { A = 1.30E+05 n = 2.50 E = 20.92 } T26f: A1CH2OH-C7H8O + OH -> A1CH2O-C7H7O + H2O { A = 6.30E+06 n = 2.00 E = 6.28 } T27f: A1CH2OH-C7H8O + CH3 -> A1CH2O-C7H7O + CH4 { A = 1.00E+07 n = 1.50 E = 41.59 } # Choi, Xia, Park & Lin 2000 # Xia & Lin 2000 T28f: A1--C6H5 + CH2O -> A1-C6H6 + HCO { A = 8.55E+04 n = 2.19 E = 0.16 } # da Silva & Bozzelli 2009 - P=1atm T29f: A1CH2O-C7H7O -> A1CHO-C7H6O + H { A = 5.26E+28 n = -5.08 E = 93.09 } T30f: A1CH2O-C7H7O -> A1--C6H5 + CH2O { A = 7.21E+33 n = -6.21 E = 154.18 } T31f: A1CH2O-C7H7O -> A1-C6H6 + HCO { A = 2.37E+32 n = -6.10 E = 120.54 } # From CH3O+R->CH2O+RH (x2/3) T32f: A1CH2O-C7H7O + H -> A1CHO-C7H6O + H2 { A = 1.33E+13 n = .00 E = .00 } T33f: A1CH2O-C7H7O + O -> A1CHO-C7H6O + OH { A = 6.67E+12 n = .00 E = .00 } T34f: A1CH2O-C7H7O + OH -> A1CHO-C7H6O + H2O { A = 3.33E+12 n = .00 E = .00 } # From CH3O (x2/3) T35f: A1CH2O-C7H7O + O2 -> A1CHO-C7H6O + HO2 { A = 2.85E-13 n = 7.60 E = -14.77 } # Benzaldehyde # ------------ # From CH3CHO - Baulch et al. 2005 # Grela & Colussi 1986 - Loss of H then loss of CO T36 : A1CHO-C7H6O -> A1--C6H5 + CO + H { A = 2.10E+16 n = .00 E = 342.00 } # From CH3CHO # Baulch et al. 2005 T37 : A1CHO-C7H6O + H -> A1--C6H5 + CO + H2 { A = 4.09E+09 n = 1.16 E = 10.06 } T38 : A1CHO-C7H6O + O -> A1--C6H5 + CO + OH { A = 5.84E+12 n = .00 E = 7.57 } T39 : A1CHO-C7H6O + OH -> A1--C6H5 + CO + H2O { A = 2.89E+08 n = 1.35 E = -6.58 } T40 : A1CHO-C7H6O + O2 -> A1--C6H5 + CO + HO2 { A = 1.20E+05 n = 2.50 E = 157.13 } T41 : A1CHO-C7H6O + HO2 -> A1--C6H5 + CO + H2O2 { A = 4.09E+04 n = 2.50 E = 42.69 } T42 : A1CHO-C7H6O + CH3 -> A1--C6H5 + CO + CH4 { A = 3.49E-08 n = 6.21 E = 6.82 } # Cresol # All isomers lumped into meta # ---------------------------- # From A1OH/A1O T43f: HOA1CH3-C7H8O -> OA1CH3-C7H7O + H { A = 1.01E+71 n =-15.92 E = 522.12 } T44f: HOA1CH3-C7H8O + H -> OA1CH3-C7H7O + H2 { A = 1.15E+14 n = .00 E = 51.87 } T45f: HOA1CH3-C7H8O + O -> OA1CH3-C7H7O + OH { A = 2.81E+13 n = .00 E = 30.76 } T46f: HOA1CH3-C7H8O + OH -> OA1CH3-C7H7O + H2O { A = 2.95E+06 n = 2.00 E = -5.49 } T47 : OA1CH3-C7H7O -> C5H4CH2 + CO + H { A = 2.90E+10 n = .00 E = 152.40 } # Methyl-phenyl # All isomers lumped into meta # ---------------------------- # From A1 (x0.65) # From symmetry should be x5/6 # Seta, Nakajima & Miyoshi 2006 - Rate for OH - Same as A1 x0.65 T50f: A1CH3-C7H8 -> A1CH3*-C7H7 + H { A = 8.39E+60 n =-12.48 E = 619.59 } T51f: A1CH3-C7H8 + H -> A1CH3*-C7H7 + H2 { A = 3.91E+08 n = 1.80 E = 68.42 } T52f: A1CH3-C7H8 + O -> A1CH3*-C7H7 + OH { A = 2.60E+13 n = .00 E = 61.50 } T53f: A1CH3-C7H8 + OH -> A1CH3*-C7H7 + H2O { A = 1.36E+04 n = 2.69 E = 2.59 } T54f: A1CH3-C7H8 + CH3 -> A1CH3*-C7H7 + CH4 { A = 1.79E-02 n = 4.46 E = 57.06 } # From A1- T55f: A1CH3*-C7H7 + O -> OA1CH3-C7H7O { A = 1.00E+14 n = .00 E = .00 } T56f: A1CH3*-C7H7 + OH -> OA1CH3-C7H7O + H { A = 3.00E+13 n = .00 E = .00 } T57f: A1CH3*-C7H7 + HO2 -> OA1CH3-C7H7O + OH { A = 3.00E+13 n = .00 E = .00 } # da Silva, Chen & Bozzelli 2007 # Assumed products for methyloxepinoxy decomposition T58f: A1CH3*-C7H7 + O2 -> OA1CH3-C7H7O + O { A = 8.57E+20 n = -2.27 E = 30.08 } T59 : A1CH3*-C7H7 + O2 -> C5H4CH2 + CO2 + H { A = 2.55E+13 n = -0.44 E = -6.90 } T60 : A1CH3*-C7H7 + O2 -> P-C3H4 + C2H3 + CO + CO { A = 2.55E+13 n = -0.44 E = -6.90 } #==========================================================================# # # # Ethyl-Benzene chemistry # # # # Adapted from C3H8 and Toluene/Benzene chemistry # # # #==========================================================================# # Ethylbenzene # ------------ # Estimated from C3H7+H - HPL E01f: A1C2H4-C8H9 + H -> A1C2H5-C8H10 { A = 3.61E+13 n = .00 E = .00 } # Estimated from C2H5+CH3 - HPL E02f: A1CH2-C7H7 + CH3 -> A1C2H5-C8H10 { A = 2.00E+13 n = .00 E = .00 } E03f: A1--C6H5 + C2H5 -> A1C2H5-C8H10 { A = 2.00E+13 n = .00 E = .00 } # From A1CH3 E04f: A1C2H5-C8H10 + H -> A1-C6H6 + C2H5 { A = 2.31E+06 n = 2.17 E = 17.42 } E05f: A1C2H5-C8H10 + OH -> A1OH-C6H6O + C2H5 { A = 7.83E+02 n = 2.88 E = 13.48 } # From C3H8 (x0.5) E06f: A1C2H5-C8H10 + H -> A1C2H4-C8H9 + H2 { A = 4.68E+07 n = 1.97 E = 34.31 } E07f: A1C2H5-C8H10 + O -> A1C2H4-C8H9 + OH { A = 9.95E+04 n = 2.68 E = 15.55 } E08f: A1C2H5-C8H10 + OH -> A1C2H4-C8H9 + H2O { A = 2.67E+03 n = 2.94 E = -1.75 } E09f: A1C2H5-C8H10 + CH3 -> A1C2H4-C8H9 + CH4 { A = 4.52E-01 n = 3.65 E = 29.93 } # From C2H6 E10f: A1C2H5-C8H10 + HO2 -> A1C2H4-C8H9 + H2O2 { A = 2.61E+02 n = 3.37 E = 66.58 } # Ethylbenzene radicals # --------------------- # Tokmakov & Lin 2004 # HPL for both decompositions E11 : A1C2H4-C8H9 -> A1--C6H5 + C2H4 { A = 1.72E+11 n = 0.78 E = 161.94 } E12 : A1C2H4-C8H9 -> A1C2H3-C8H8 + H { A = 3.79E+06 n = 1.99 E = 134.33 } # From C3H7 E13f: A1C2H4-C8H9 + H -> A1C2H3-C8H8 + H2 { A = 1.80E+12 n = .00 E = .00 } E14f: A1C2H4-C8H9 + OH -> A1C2H3-C8H8 + H2O { A = 2.41E+13 n = .00 E = .00 } E15f: A1C2H4-C8H9 + CH3 -> A1C2H3-C8H8 + CH4 { A = 3.31E+12 n = .00 E = -3.22 } E16f: A1C2H4-C8H9 + O -> A1CH2-C7H7 + CH2O { A = 9.60E+13 n = .00 E = .00 } # From NC7 E17 : A1C2H4-C8H9 + HO2 -> A1CH2-C7H7 + CH2O + OH { A = 7.00E+12 n = .00 E = -4.18 } E18 : A1C2H4-C8H9 + CH3O2 -> A1CH2-C7H7 + CH2O + CH3O { A = 7.00E+12 n = .00 E = -4.18 } #===============================================================================# # # # Styrene Chemistry # # Adapted from C2H4 chemistry # # Additional rates from Kislov & Mebel 2005 # # # #===============================================================================# # Styrene # ------- # Greda et al. 1992 ST01 : A1C2H3-C8H8 -> A1-C6H6 + H2C2 { A = 2.40E+14 n = .00 E = 326.90 } # Wang & Frenklach 1997 - estimated HPL ST02f: A1--C6H5 + C2H3 -> A1C2H3-C8H8 { A = 6.00E+12 n = .00 E = .00 } # Tokmakov & Lin 2004 ST03f: A1C2H3-C8H8 + H -> A1--C6H5 + C2H4 { A = 3.62E+28 n = -4.24 E = 99.85 } ST04f: A1C2H3-C8H8 + H -> A1-C6H6 + C2H3 { A = 5.62E+24 n = -3.00 E = 82.97 } # From A1CH3 ST05f: A1C2H3-C8H8 + OH -> A1OH-C6H6O + C2H3 { A = 7.83E+02 n = 2.88 E = 13.48 } # From C2H4 (x0.5) ST06f: A1C2H3-C8H8 -> A1C2H2-C8H7 + H { A = 3.01E+14 n = 0.34 E = 465.49 } ST07f: A1C2H3-C8H8 + H -> A1C2H2-C8H7 + H2 { A = 6.35E+04 n = 2.75 E = 48.74 } ST08f: A1C2H3-C8H8 + OH -> A1C2H2-C8H7 + H2O { A = 1.12E+04 n = 2.75 E = 9.27 } # From A1 (x1/3) ST09f: A1C2H3-C8H8 -> A1C2H3*-C8H7 + H { A = 4.30E+60 n =-12.48 E = 619.59 } ST10f: A1C2H3-C8H8 + H -> A1C2H3*-C8H7 + H2 { A = 2.01E+08 n = 1.80 E = 68.42 } ST11f: A1C2H3-C8H8 + OH -> A1C2H3*-C8H7 + H2O { A = 7.80E+03 n = 2.68 E = 3.07 } # From C2H4 (x0.5) # Half for each carbon atoms ST12f: A1C2H3-C8H8 + O -> A1CH2-C7H7 + HCO { A = 5.10E+07 n = 1.66 E = 2.75 } ST13f: A1C2H3-C8H8 + O -> A1CHO-C7H6O + T-CH2 { A = 3.58E+04 n = 2.47 E = 3.89 } ST14f: A1C2H3-C8H8 + OH -> A1CH2-C7H7 + CH2O { A = 1.88E+36 n = -7.80 E = 29.54 } ST15f: A1C2H3-C8H8 + OH -> A1CHO-C7H6O + CH3 { A = 1.88E+36 n = -7.80 E = 29.54 } # Styryl radical # -------------- # Kislov & Mebel 2005 ST20f: A1--C6H5 + C2H2 -> A1C2H2-C8H7 { A = 3.29E+06 n = 2.05 E = 13.23 } ST21f: A1C2H2-C8H7 -> A1C2H3*-C8H7 { A = 5.90E+10 n = 0.55 E = 115.34 } ST22f: A1C2H2-C8H7 -> A1C2H-C8H6 + H { A = 1.44E+11 n = 1.02 E = 161.81 } ST23f: A1C2H2-C8H7 + H -> A1C2H-C8H6 + H2 { A = 3.29E+11 n = 0.49 E = 44.48 } # From C2H3 (x1/2) ST24f: A1C2H2-C8H7 + OH -> A1C2H-C8H6 + H2O { A = 2.50E+12 n = .00 E = .00 } ST25f: A1C2H2-C8H7 + O2 -> A1C2H-C8H6 + HO2 { A = 6.70E+05 n = 1.61 E = -1.61 } # From C2H3 + O ST26f: A1C2H2-C8H7 + O -> A1CH2-C7H7 + CO { A = 1.03E+13 n = 0.21 E = -1.79 } # From C2H3 + O2 ST27 : A1C2H2-C8H7 + O2 -> A1CH2-C7H7 + CO + O { A = 3.03E+11 n = 0.29 E = 0.05 } ST28f: A1C2H2-C8H7 + O2 -> A1CHO-C7H6O + HCO { A = 4.58E+16 n = -1.39 E = 4.25 } # Ethynylbenzene # -------------- # From A1 (x1/3) ST30f: A1C2H-C8H6 -> A1C2H*-C8H5 + H { A = 4.30E+60 n =-12.48 E = 619.59 } ST31f: A1C2H-C8H6 + H -> A1C2H*-C8H5 + H2 { A = 2.01E+08 n = 1.80 E = 68.42 } ST32f: A1C2H-C8H6 + OH -> A1C2H*-C8H5 + H2O { A = 7.80E+03 n = 2.68 E = 3.07 } # From C2H2 ST33f: A1C2H-C8H6 + O -> A1--C6H5 + HCCO { A = 4.05E+06 n = 2.00 E = 7.95 } ST34f: A1C2H-C8H6 + OH -> A1--C6H5 + HCCOH { A = 1.21E+06 n = 2.00 E = 53.19 } ST35f: A1C2H-C8H6 + OH -> A1--C6H5 + CH2CO { A = 3.77E+06 n = 1.55 E = 8.81 } ST36f: A1C2H-C8H6 + OH -> A1CH2-C7H7 + CO { A = 6.40E+08 n = 0.73 E = 10.79 } #T34f: A1C2H-C8H6 + OH -> A1-C6H6 + HCCO { A = 1.00E+13 n = .00 E = .00 } #=========================================================================# # # # Xylene Oxidation Chemistry # # Adapted from Toluene Chemistry # # # #=========================================================================# # Xylene # ------ # From A1CH3 (x2) XY00f: A1CH3CH3-C8H10 -> A1CH3CH2-C8H9 + H { A = 2.50E+18 n = -0.60 E = 396.59 } XY01f: A1CH3CH3-C8H10 -> A1CH3*-C7H7 + CH3 { A = 4.32E+29 n = -3.58 E = 460.93 } # From A1CH3+R (x2) XY02f: A1CH3CH3-C8H10 + H -> A1CH3CH2-C8H9 + H2 { A = 1.29E+01 n = 3.98 E = 14.16 } XY03f: A1CH3CH3-C8H10 + O -> A1CH3CH2-C8H9 + OH { A = 2.36E+00 n = 4.09 E = 10.65 } XY04f: A1CH3CH3-C8H10 + OH -> A1CH3CH2-C8H9 + H2O { A = 3.54E+05 n = 2.39 E = -2.52 } XY05f: A1CH3CH3-C8H10 + O2 -> A1CH3CH2-C8H9 + HO2 { A = 4.36E+07 n = 2.50 E = 192.65 } XY06f: A1CH3CH3-C8H10 + HO2 -> A1CH3CH2-C8H9 + H2O2 { A = 1.87E+05 n = 2.50 E = 61.44 } XY07f: A1CH3CH3-C8H10 + CH3 -> A1CH3CH2-C8H9 + CH4 { A = 8.44E+14 n = .00 E = 93.12 } # From A1CH3+X (x2) XY09f: A1CH3CH3-C8H10 + H -> A1CH3-C7H8 + CH3 { A = 4.62E+06 n = 2.17 E = 17.42 } XY10f: A1CH3CH3-C8H10 + OH -> HOA1CH3-C7H8O + CH3 { A = 1.57E+03 n = 2.88 E = 13.48 } # !!!! CAREFUL !!!! # Path from Bounaceur et al. 2005 # Rate from A1+O (x2/3) XY11 : A1CH3CH3-C8H10 + O -> A1CH3-C7H8 + CO + 2H { A = 1.82E+08 n = 1.55 E = 12.93 } # Xylyl radical # ------------- # Path from Bournaceur et al. 2005 # Rate from A1CH2 XY12 : A1CH3CH2-C8H9 -> A1-C6H6 + H + C2H2 { A = 8.20E+14 n = .00 E = 337.55 } XY13f: A1CH3CH2-C8H9 + H -> A1CH3*-C7H7 + CH3 { A = 5.83E+67 n =-14.15 E = 285.89 } # Total rate from A1CH2+O # Branching ratio from A1CH2O decomposition XY14f: A1CH3CH2-C8H9 + O -> A1CH3CHO-C8H8O + H { A = 4.37e+18 n = -1.34 E = 6.66 } XY15f: A1CH3CH2-C8H9 + O -> A1CH3*-C7H7 + CH2O { A = 5.99E+23 n = -2.47 E = 67.75 } XY16f: A1CH3CH2-C8H9 + O -> A1CH3-C7H8 + HCO { A = 1.97E+22 n = -2.36 E = 34.11 } XY17 : A1CH3CH2-C8H9 + OH -> A1CH3CHO-C8H8O + H2 { A = 2.00E+13 n = .00 E = .00 } # From A1CH2+O2 # Addition from Murakami et al. 2009 # Peroxy isomerization from Canneaux et al. 2008 XY18f: A1CH3CH2-C8H9 + O2 -> A1CH3CHO-C8H8O + OH { A = 1.38E+02 n = 2.42 E = 31.13 } XY19f: A1CH3CH2-C8H9 + O2 -> OA1CH3-C7H7O + CH2O { A = 6.57E+03 n = 1.87 E = 20.93 } # Total rate from A1CH2+O # Branching ratio from A1CH2O decomposition XY201: A1CH3CH2-C8H9 + HO2 -> A1CH3CHO-C8H8O + H + OH { A = 2.28E+13 n = -0.31 E = -2.75 } XY202: A1CH3CH2-C8H9 + HO2 -> A1CH3*-C7H7 + CH2O + OH { A = 3.13E+18 n = -1.44 E = 58.34 } XY203: A1CH3CH2-C8H9 + HO2 -> A1CH3-C7H8 + HCO + OH { A = 1.03E+17 n = -1.33 E = 24.70 } # From A-C3H5 + C3H3 XY22 : A1CH3CH2-C8H9 + C3H3 -> A2CH3-C11H10 + 2H { A = 1.88E+38 n = -7.53 E = 99.91 } # Tolualdehyde # ------------ # From A1CH3 & A1CHO decomposition XY23f: A1CH3CHO-C8H8O -> A1CHOCH2-C8H7O + H { A = 1.25E+18 n = -0.60 E = 396.59 } XY24 : A1CH3CHO-C8H8O -> A1--C6H5 + CO + CH3 { A = 2.16E+29 n = -3.58 E = 460.93 } XY25 : A1CH3CHO-C8H8O -> A1CH3*-C7H7 + CO + H { A = 2.10E+16 n = .00 E = 342.00 } # From A1CH3+R XY26f: A1CH3CHO-C8H8O + H -> A1CHOCH2-C8H7O + H2 { A = 6.47E+00 n = 3.98 E = 14.16 } XY27f: A1CH3CHO-C8H8O + O -> A1CHOCH2-C8H7O + OH { A = 1.18E+00 n = 4.09 E = 10.65 } XY28f: A1CH3CHO-C8H8O + OH -> A1CHOCH2-C8H7O + H2O { A = 1.77E+05 n = 2.39 E = -2.52 } XY29f: A1CH3CHO-C8H8O + O2 -> A1CHOCH2-C8H7O + HO2 { A = 2.18E+07 n = 2.50 E = 192.65 } XY30f: A1CH3CHO-C8H8O + HO2 -> A1CHOCH2-C8H7O + H2O2 { A = 9.33E+04 n = 2.50 E = 61.44 } XY31f: A1CH3CHO-C8H8O + CH3 -> A1CHOCH2-C8H7O + CH4 { A = 4.22E+14 n = .00 E = 93.12 } # From A1CHO+R XY33 : A1CH3CHO-C8H8O + H -> A1CH3*-C7H7 + CO + H2 { A = 4.09E+09 n = 1.16 E = 10.06 } XY34 : A1CH3CHO-C8H8O + O -> A1CH3*-C7H7 + CO + OH { A = 5.84E+12 n = .00 E = 7.57 } XY35 : A1CH3CHO-C8H8O + OH -> A1CH3*-C7H7 + CO + H2O { A = 2.89E+08 n = 1.35 E = -6.58 } XY36 : A1CH3CHO-C8H8O + O2 -> A1CH3*-C7H7 + CO + HO2 { A = 1.20E+05 n = 2.50 E = 157.13 } XY37 : A1CH3CHO-C8H8O + HO2 -> A1CH3*-C7H7 + CO + H2O2 { A = 4.09E+04 n = 2.50 E = 42.69 } XY38 : A1CH3CHO-C8H8O + CH3 -> A1CH3*-C7H7 + CO + CH4 { A = 3.49E-08 n = 6.21 E = 6.82 } # From A1CH3+H - substitution XY39f: A1CH3CHO-C8H8O + H -> A1CH3-C7H8 + HCO { A = 2.31E+06 n = 2.17 E = 17.42 } XY40f: A1CH3CHO-C8H8O + H -> A1CHO-C7H6O + CH3 { A = 2.31E+06 n = 2.17 E = 17.42 } # From A1CH3+OH - substitution XY41f: A1CH3CHO-C8H8O + OH -> HOA1CH3-C7H8O + HCO { A = 7.83E+02 n = 2.88 E = 13.48 } XY42 : A1CH3CHO-C8H8O + OH -> A1O-C6H5O + H + CO + CH3 { A = 7.83E+02 n = 2.88 E = 13.48 } # Tolualdehyde radical # -------------------- # Total rate from A1CH2+O # Branching ratio from A1CH2O decomposition XY43f: A1CHOCH2-C8H7O + O -> A1CHOCHO-C8H6O2 + H { A = 4.37e+18 n = -1.34 E = 6.66 } XY44 : A1CHOCH2-C8H7O + O -> A1--C6H5 + CO + CH2O { A = 5.99E+23 n = -2.47 E = 67.75 } XY45f: A1CHOCH2-C8H7O + O -> A1CHO-C7H6O + HCO { A = 1.97E+22 n = -2.36 E = 34.11 } XY46 : A1CHOCH2-C8H7O + OH -> A1CHOCHO-C8H6O2 + H2 { A = 2.00E+13 n = .00 E = .00 } XY47f: A1CHOCH2-C8H7O + O2 -> A1CHOCHO-C8H6O2 + OH { A = 1.38E+02 n = 2.42 E = 31.98 } XY48 : A1CHOCH2-C8H7O + HO2 -> A1CHOCHO-C8H6O2 + OH + H { A = 1.19E+09 n = 1.03 E = -9.41 } # Phthalaldehyde # -------------- # From A1CHO decomposition (x2) XY50 : A1CHOCHO-C8H6O2 -> A1--C6H5 + 2 CO + H { A = 4.20E+16 n = .00 E = 342.00 } # From A1CHO+R (x2) XY51 : A1CHOCHO-C8H6O2 + H -> A1CHO-C7H6O + CO + H { A = 8.18E+09 n = 1.16 E = 10.06 } XY52 : A1CHOCHO-C8H6O2 + O -> A1CHO-C7H6O + CO + O { A = 1.17E+13 n = .00 E = 7.57 } XY53 : A1CHOCHO-C8H6O2 + OH -> A1CHO-C7H6O + CO + OH { A = 5.78E+08 n = 1.35 E = -6.58 } XY54 : A1CHOCHO-C8H6O2 + O2 -> A1CHO-C7H6O + CO + O2 { A = 2.40E+05 n = 2.50 E = 157.13 } XY55 : A1CHOCHO-C8H6O2 + HO2 -> A1CHO-C7H6O + CO + HO2 { A = 8.18E+04 n = 2.50 E = 42.69 } XY56 : A1CHOCHO-C8H6O2 + CH3 -> A1CHO-C7H6O + CO + CH3 { A = 6.98E-08 n = 6.21 E = 6.82 } # From A1CH3+X (x2) - substitution XY57f: A1CHOCHO-C8H6O2 + H -> A1CHO-C7H6O + HCO { A = 4.62E+06 n = 2.17 E = 17.42 } XY58 : A1CHOCHO-C8H6O2 + OH -> A1O-C6H5O + H + CO + HCO { A = 1.57E+03 n = 2.88 E = 13.48 } #=========================================================================# # # # alpha-MethylNaphthalene chemistry # # Adapted from Toluene chemistry # # # #=========================================================================# # MethylNaphthalene # ----------------- N01f: A2CH3-C11H10 + H -> A2-C10H8 + CH3 { A = 2.31E+06 n = 2.17 E = 17.42 } N02f: A2CH3-C11H10 + OH -> A2OH-C10H8O + CH3 { A = 7.83E+02 n = 2.88 E = 13.48 } # Collision Limit at 298K N04f: A2CH3-C11H10 -> A2CH2-C11H9 + H { A = 1.25E+18 n = -0.60 E = 396.59 } N05f: A2CH3-C11H10 -> A2--C10H7 + CH3 { A = 3.20E+34 n = -5.02 E = 478.03 } N06f: A2CH2-C11H9 + H -> A2--C10H7 + CH3 { A = 5.83E+67 n =-14.15 E = 285.89 } N07f: A2CH2-C11H9 -> C9H7 + C2H2 { A = 8.20E+14 n = .00 E = 337.55 } N08f: A2CH3-C11H10 + H -> A2CH2-C11H9 + H2 { A = 6.47E+00 n = 3.98 E = 14.16 } N09f: A2CH3-C11H10 + O -> A2CH2-C11H9 + OH { A = 1.18E+00 n = 4.09 E = 10.65 } N10f: A2CH3-C11H10 + OH -> A2CH2-C11H9 + H2O { A = 1.77E+05 n = 2.39 E = -2.52 } N11f: A2CH3-C11H10 + O2 -> A2CH2-C11H9 + HO2 { A = 2.18E+07 n = 2.50 E = 192.65 } N12f: A2CH3-C11H10 + CH3 -> A2CH2-C11H9 + CH4 { A = 4.22E+14 n = .00 E = 93.12 } N13f: A2CH3-C11H10 + HO2 -> A2CH2-C11H9 + H2O2 { A = 9.33E+04 n = 2.50 E = 61.44 } N14 : A2CH3-C11H10 + O -> A2-C10H8 + CO + 2 H { A = 1.10E+13 n = .00 E = 18.96 } N15 : A2CH3-C11H10 + O -> C9H7 + CH3 + CO { A = 1.47E+13 n = .00 E = 18.96 } # Methylene-Naphthyl # ------------------ N16f: A2CH2-C11H9 + O -> A2CH2O-C11H9O { A = 2.28E+14 n = .00 E = .00 } N17 : A2CH2-C11H9 + OH -> A2CH2O-C11H9O + H { A = 2.00E+13 n = .00 E = .00 } N18f: A2CH2-C11H9 + HO2 -> A2CH2O-C11H9O + OH { A = 1.19E+09 n = 1.03 E = -9.41 } # From A-C3H5 + C3H3 N18 : A2CH2-C11H9 + C3H3 -> A3-C14H10 + 2H { A = 1.88E+38 n = -7.53 E = 99.91 } N20f: A2CH2-C11H9 + O2 -> A2CHO-C11H8O + OH { A = 3.76E+15 n = -1.55 E = 47.37 } N21f: A2CH2-C11H9 + O2 -> A2O-C10H7O + CH2O { A = 3.08E+09 n = 0.37 E = 70.75 } # Methoxy-Naphthyl # ---------------- N22f: A2CH2O-C11H9O -> A2CHO-C11H8O + H { A = 5.26E+28 n = -5.08 E = 93.09 } N23f: A2CH2O-C11H9O -> A2--C10H7 + CH2O { A = 7.21E+33 n = -6.21 E = 154.18 } N24f: A2CH2O-C11H9O + H -> A2CHO-C11H8O + H2 { A = 1.33E+13 n = .00 E = .00 } N25f: A2CH2O-C11H9O + O -> A2CHO-C11H8O + OH { A = 6.67E+12 n = .00 E = .00 } N26f: A2CH2O-C11H9O + OH -> A2CHO-C11H8O + H2O { A = 3.33E+12 n = .00 E = .00 } N27f: A2CH2O-C11H9O + O2 -> A2CHO-C11H8O + HO2 { A = 2.85E-13 n = 7.60 E = -14.77 } # Naphthaldehyde # -------------- N28 : A2CHO-C11H8O -> A2--C10H7 + CO + H { A = 2.10E+16 n = .00 E = 342.00 } N29 : A2CHO-C11H8O + H -> A2--C10H7 + CO + H2 { A = 4.09E+09 n = 1.16 E = 10.06 } N30 : A2CHO-C11H8O + O -> A2--C10H7 + CO + OH { A = 5.84E+12 n = .00 E = 7.57 } N31 : A2CHO-C11H8O + OH -> A2--C10H7 + CO + H2O { A = 2.89E+08 n = 1.35 E = -6.58 } N32 : A2CHO-C11H8O + O2 -> A2--C10H7 + CO + HO2 { A = 1.20E+05 n = 2.50 E = 157.13 } N33 : A2CHO-C11H8O + HO2 -> A2--C10H7 + CO + H2O2 { A = 4.09E+04 n = 2.50 E = 42.69 } N34 : A2CHO-C11H8O + CH3 -> A2--C10H7 + CO + CH4 { A = 3.49E-08 n = 6.21 E = 6.82 } #==========================================================================# # # # Benzene Oxidation Chemistry # # # # "Detailed kinetic modeling of benzene and toluene oxidation # # at high temperatures" # # Zoran M. Djurisic - Master's Thesis # # http://diesel.me.berkeley.edu/~zoran/publications/2000_MS_Thesis/ # # # #==========================================================================# ########## Benzene oxidation ########## # Benzene # ------- # Miller & Klippenstein 2003 (1bar) # Updated to include HPL from Harding et al. 2005 OX00f: A1-C6H6 -> A1--C6H5 + H { A = 1.29E+61 n =-12.48 E = 619.59 } # Wang et al. 2000 OX01f: A1--C6H5 + M9 -> O-C6H4 + H + M9 { A = 1.00E+84 n =-18.87 E = 376.98 Ai= 4.30E+12 ni= 0.62 Ei= 323.43 fcA = 0.098 fctA = 696 fcb = 0.902 fctb = 358 fcc = 1.0 fctc = 3856 } OX02f: C4H2 + C2H2 -> O-C6H4 { A = 5.00E+78 n =-19.31 E = 284.18 } # Mebel & Lin 1997 OX03f: A1-C6H6 + H -> A1--C6H5 + H2 { A = 6.02E+08 n = 1.80 E = 68.42 } # Seta, Nakajima & Miyoshi 2006 OX04f: A1-C6H6 + OH -> A1--C6H5 + H2O { A = 2.34E+04 n = 2.68 E = 3.07 } OX05f: A1-C6H6 + OH -> A1OH-C6H6O + H { A = 1.32E+02 n = 3.25 E = 23.39 } # From C2H4 + O2 (x1.5) # Hua, Ruscic, Wang 2005 # Backward ~ 2e12 OX06f: A1-C6H6 + O2 -> A1--C6H5 + HO2 { A = 4.34E+14 n = .00 E = 269.00 } # Taatjes, Wang, et al. 2010 # Refitted OX07f: A1-C6H6 + O -> A1O-C6H5O + H { A = 1.99E+07 n = 1.80 E = 16.63 } OX08f: A1-C6H6 + O -> A1OH-C6H6O { A = 2.03E+12 n = 0.30 E = 18.42 } OX09f: A1-C6H6 + O -> C5H6 + CO { A = 5.80E+16 n = -0.77 E = 63.98 } # Lindsted & Skevis 1994 (x2.0) OX10f: A1-C6H6 + O -> A1--C6H5 + OH { A = 4.00E+13 n = .00 E = 61.50 } # Phenyl radical # -------------- # da Silva, Chen & Bozzelli 2007 # From 3/4-methylphenyl + O2 OX11f: A1--C6H5 + O2 -> A1O-C6H5O + O { A = 8.57E+20 n = -2.27 E = 30.08 } # Frank, Herzler, Just & Wahl 1994 OX12f: A1--C6H5 + O2 -> OC6H4O + H { A = 3.00E+13 n = .00 E = 37.58 } OX13f: A1--C6H5 + O -> A1O-C6H5O { A = 1.00E+14 n = .00 E = .00 } OX14f: A1--C6H5 + OH -> A1O-C6H5O + H { A = 3.00E+13 n = .00 E = .00 } OX15f: A1--C6H5 + HO2 -> A1O-C6H5O + OH { A = 3.00E+13 n = .00 E = .00 } # Tokmakov & Lin 1999/2002 OX16f: A1--C6H5 + CH4 -> A1-C6H6 + CH3 { A = 3.89E-03 n = 4.57 E = 22.00 } # Phenol # ------ # Xu & Lin 2006 # Rates for 1 atm # Formation of CO x0.765 to better match Horn & Roy 1989 OX17f: A1OH-C6H6O -> C5H6 + CO { A = 6.59E+15 n = -0.61 E = 310.11 } OX18f: A1OH-C6H6O -> A1O-C6H5O + H { A = 1.01E+71 n =-15.92 E = 522.12 } # From CH3OH+R # Jodkowski, Rayez, & Rayez 1999 OX19f: A1OH-C6H6O + H -> A1O-C6H5O + H2 { A = 6.83E+01 n = 3.40 E = 30.26 } OX20f: A1OH-C6H6O + OH -> A1O-C6H5O + H2O { A = 1.73E+01 n = 3.40 E = -4.78 } OX21f: A1OH-C6H6O + CH3 -> A1O-C6H5O + CH4 { A = 3.70E-04 n = 4.70 E = 20.20 } # Brezinsky et al. 1998 OX22f: A1OH-C6H6O + O2 -> A1O-C6H5O + HO2 { A = 7.32E+13 n = .00 E = 173.22 } # Phenoxy radical # 2-B1 state for O=C6H5 # --------------------- # Murakami et al. 2003 OX23f: A1O-C6H5O -> CO + C5H5 { A = 2.90E+10 n = .00 E = 152.40 } # From C2H5 + O (x2) OX24f: A1O-C6H5O + O -> OC6H4O + H { A = 6.34E+13 n = 0.03 E = -1.65 } # From A-C3H5 + O2 - Total rate (x3/2) OX25f: A1O-C6H5O + O2 -> OC6H4O + OH { A = 6.51E+07 n = 1.30 E = 73.92 } # p-Benzoquinone # Thermoprop & Reactions for para # ------------------------------- OX26f: OC6H4O -> C5H4O + CO { A = 7.40E+11 n = .00 E = 246.86 } OX27f: OC6H4O + H -> T-C5H5O + CO { A = 4.30E+09 n = 1.45 E = 16.18 } OX28 : OC6H4O + O -> CH2CO + C2H2 + 2 CO { A = 3.00E+13 n = .00 E = 20.92 } ########## Naphthalene oxidation ########## # Naphthalene # 5/3 of the rate for A1 # ---------------------- OX30f: A2-C10H8 + O -> A2O-C10H7O + H { A = 1.83E+13 n = .00 E = 18.95 } OX31f: A2-C10H8 + O -> A2OH-C10H8O { A = 1.83E+13 n = .00 E = 18.95 } OX32f: A2-C10H8 + OH -> A2OH-C10H8O + H { A = 2.20E+02 n = 3.25 E = 23.39 } # Naphthyl radical # Full rate for A1- # ----------------- OX33f: A2--C10H7 + O2 -> A2O-C10H7O + O { A = 8.57E+20 n = -2.27 E = 30.08 } OX34f: A2*-C10H7 + O2 -> A2O-C10H7O + O { A = 8.57E+20 n = -2.27 E = 30.08 } OX35 : A2--C10H7 + O2 -> C9H6O + CO + H { A = 3.00E+13 n = .00 E = 37.58 } OX36 : A2*-C10H7 + O2 -> C9H6O + CO + H { A = 3.00E+13 n = .00 E = 37.58 } OX37f: A2--C10H7 + O -> A2O-C10H7O { A = 1.00E+14 n = .00 E = .00 } OX38f: A2*-C10H7 + O -> A2O-C10H7O { A = 1.00E+14 n = .00 E = .00 } OX39f: A2--C10H7 + OH -> A2O-C10H7O + H { A = 3.00E+13 n = .00 E = .00 } OX40f: A2*-C10H7 + OH -> A2O-C10H7O + H { A = 3.00E+13 n = .00 E = .00 } # Naphthol # Full rate for A1OH # ------------------ OX41f: A2OH-C10H8O -> C9H8 + CO { A = 8.62E+15 n = -0.61 E = 310.11 } OX42f: A2OH-C10H8O -> A2O-C10H7O + H { A = 1.01E+71 n =-15.92 E = 522.12 } OX43f: A2OH-C10H8O + H -> A2O-C10H7O + H2 { A = 6.83E+01 n = 3.40 E = 30.26 } OX44f: A2OH-C10H8O + OH -> A2O-C10H7O + H2O { A = 1.73E+01 n = 3.40 E = -4.78 } OX45f: A2OH-C10H8O + CH3 -> A2O-C10H7O + CH4 { A = 3.70E-04 n = 4.70 E = 20.20 } # Naphthoxy radical # Full rate for A1O # ----------------- OX46f: A2O-C10H7O -> C9H7 + CO { A = 2.90E+10 n = .00 E = 152.40 } OX47 : A2O-C10H7O + O -> C9H6O + CO + H { A = 1.68E+14 n = .00 E = .00 } OX48 : A2O-C10H7O + O2 -> C9H6O + CO + OH { A = 6.51E+07 n = 1.30 E = 73.92 } ########## Higher PAH oxidation ########## # From A1-+O2 OX50 : A3--C14H9 + O2 -> A2C2H2B-C12H9 + 2CO { A = 8.57E+20 n = -2.27 E = 30.08 } OX51 : A3*-C14H9 + O2 -> A2C2H2A-C12H9 + 2CO { A = 8.57E+20 n = -2.27 E = 30.08 } OX52 : A4--C16H9 + O2 -> A3--C14H9 + 2CO { A = 8.57E+20 n = -2.27 E = 30.08 } OX53 : A2R5--C12H7 + O2 -> A2--C10H7 + 2CO { A = 8.57E+20 n = -2.27 E = 30.08 } OX54 : A3R5--C16H9 + O2 -> A3--C14H9 + 2CO { A = 8.57E+20 n = -2.27 E = 30.08 } # From A1+OH # Rescaled by number of active sites OX60 : A3-C14H10 + OH -> A2C2HA-C12H8 + CH3 + CO { A = 1.10E+02 n = 3.25 E = 23.39 } OX61 : A3-C14H10 + OH -> A2C2HB-C12H8 + CH3 + CO { A = 1.10E+02 n = 3.25 E = 23.39 } OX62 : A4-C16H10 + OH -> A3-C14H10 + HCCO { A = 2.20E+02 n = 3.25 E = 23.39 } OX63 : A2R5-C12H8 + OH -> A2-C10H8 + HCCO { A = 1.76E+02 n = 3.25 E = 23.39 } OX64 : A3R5-C16H10 + OH -> A3-C14H10 + HCCO { A = 2.20E+02 n = 3.25 E = 23.39 } OX65 : A4R5-C18H10 + OH -> A4-C16H10 + HCCO { A = 2.20E+02 n = 3.25 E = 23.39 } OX66 : FLTN-C16H10 + OH -> A3-C14H10 + HCCO { A = 2.20E+02 n = 3.25 E = 23.39 } #=========================================================================# # # # NOx chemistry is taken from # # # # GRI-MECH version 3.0 # # http://www.me.berkeley.edu/gri_mech/ # # # # Gregory P. Smith, David M. Golden, Michael Frenklach, Nigel W. Moriarty # # Boris Eiteneer, Mikhail Goldenberg, C. Thomas Bowman, Ronald K. Hanson, # # Soonho Song, William C. Gardiner, Jr., Vitali V. Lissianski, Zhiwei Qin # # # #=========================================================================# /* NO01f: N + NO -> N2 + O { A = 2.70E+13 n = .00 E = 1.49 } NO02f: N + O2 -> NO + O { A = 9.000E+09 n = 1.000 E = 27.196 } NO03f: N + OH -> NO + H { A = 3.360E+13 n = 0.000 E = 1.611 } NO04f: N2O + O -> N2 + O2 { A = 1.400E+12 n = 0.000 E = 45.229 } NO05f: N2O + O -> 2 NO { A = 2.900E+13 n = 0.000 E = 96.860 } NO06f: N2O + H -> N2 + OH { A = 3.870E+14 n = 0.000 E = 78.994 } NO07f: N2O + OH -> N2 + HO2 { A = 2.000E+12 n = 0.000 E = 88.115 } NO08f: N2O + M28 -> N2 + O + M28 { Ai = 7.910E+10 ni = 0.000 Ei = 234.388 A = 6.370E+14 n = 0.000 E = 236.982 fcc = 1.0 fctc = 0.0 } NO09f: HO2 + NO -> NO2 + OH { A = 2.110E+12 n = 0.000 E = -2.008 } NO10f: NO + O + M29 -> NO2 + M29 { A = 1.060E+20 n = -1.410 E =0.000 } NO11f: NO2 + O -> NO + O2 { A = 3.900E+12 n = 0.000 E = -1.004 } NO12f: NO2 + H -> NO + OH { A = 1.320E+14 n = 0.000 E = 1.506 } NO13f: NH + O -> NO + H { A = 4.000E+13 n = 0.000 E = 0.000 } NO14f: NH + H -> N + H2 { A = 3.200E+13 n = 0.000 E = 1.381 } NO15f: NH + OH -> HNO + H { A = 2.000E+13 n = 0.000 E = 0.000 } NO16f: NH + OH -> N + H2O { A = 2.000E+09 n = 1.200 E = 0.000 } NO17f: NH + O2 -> HNO + O { A = 4.610E+05 n = 2.000 E = 27.196 } NO18f: NH + O2 -> NO + OH { A = 1.280E+06 n = 1.500 E = 0.418 } NO19f: NH + N -> N2 + H { A = 1.500E+13 n = 0.000 E = 0.000 } NO20f: NH + H2O -> HNO + H2 { A = 2.000E+13 n = 0.000 E = 57.948 } NO21f: NH + NO -> N2 + OH { A = 2.160E+13 n = -0.230 E = 0.00 } NO22f: NH + NO -> N2O + H { A = 3.650E+14 n = -0.450 E = 0.000 } NO23f: NH2 + O -> OH + NH { A = 3.000E+12 n = 0.000 E = 0.000 } NO24f: NH2 + O -> H + HNO { A = 3.900E+13 n = 0.000 E = 0.000 } NO25f: NH2 + H -> NH + H2 { A = 4.000E+13 n = 0.000 E = 15.272 } NO26f: NH2 + OH -> NH + H2O { A = 9.000E+07 n = 1.500 E = -1.925 } NO27f: NNH -> N2 + H { A = 3.300E+08 n = 0.000 E = 0.000 } NO28f: NNH + M30 -> N2 + H + M30 { A = 1.300E+14 n = -0.110 E = 20.836 } NO29f: NNH + O2 -> HO2 + N2 { A = 5.000E+12 n = 0.000 E = 0.000 } NO30f: NNH + O -> OH + N2 { A = 2.500E+13 n = 0.000 E = 0.000 } NO31f: NNH + O -> NH + NO { A = 7.000E+13 n = 0.000 E = 0.000 } NO32f: NNH + H -> H2 + N2 { A = 5.000E+13 n = 0.000 E = 0.000 } NO33f: NNH + OH -> H2O + N2 { A = 2.000E+13 n = 0.000 E = 0.000 } NO34f: NNH + CH3 -> CH4 + N2 { A = 2.500E+13 n = 0.000 E = 0.000 } NO35f: H + NO + M31 -> HNO + M31 { A = 4.480E+19 n = -1.320 E = 3.096 } NO36f: HNO + O -> NO + OH { A = 2.500E+13 n = 0.000 E = 0.000 } NO37f: HNO + H -> H2 + NO { A = 9.000E+11 n = 0.720 E = 2.761 } NO38f: HNO + OH -> NO + H2O { A = 1.300E+07 n = 1.900 E = -3.975 } NO39f: HNO + O2 -> HO2 + NO { A = 1.000E+13 n = 0.000 E = 54.392 } NO40f: CN + O -> CO + N { A = 7.700E+13 n = 0.000 E = 0.000 } NO41f: CN + OH -> NCO + H { A = 4.000E+13 n = 0.000 E = 0.000 } NO42f: CN + H2O -> HCN + OH { A = 8.000E+12 n = 0.000 E = 31.213 } NO43f: CN + O2 -> NCO + O { A = 6.140E+12 n = 0.000 E = -1.841 } NO44f: CN + H2 -> HCN + H { A = 2.950E+05 n = 2.450 E = 9.372 } NO45f: NCO + O -> NO + CO { A = 2.350E+13 n = 0.000 E = 0.000 } NO46f: NCO + H -> NH + CO { A = 5.400E+13 n = 0.000 E = 0.000 } NO47f: NCO + OH -> NO + H + CO { A = 2.500E+12 n = 0.000 E = 0.000 } NO48f: NCO + N -> N2 + CO { A = 2.000E+13 n = 0.000 E = 0.000 } NO49f: NCO + O2 -> NO + CO2 { A = 2.000E+12 n = 0.000 E = 83.680 } NO50f: NCO + M32 -> N + CO + M32 { A = 3.100E+14 n = 0.000 E =226.145 } NO51f: NCO + NO -> N2O + CO { A = 1.900E+17 n = -1.520 E = 3.09 } NO52f: NCO + NO -> N2 + CO2 { A = 3.800E+18 n = -2.000 E = 3.347 } NO53f: HCN + M33 -> H + CN + M33 { A = 1.040E+29 n = -3.300 E =529.694 } NO54f: HCN + O -> NCO + H { A = 2.030E+04 n = 2.640 E = 20.836 } NO55f: HCN + O -> NH + CO { A = 5.070E+03 n = 2.640 E = 20.836 } NO56f: HCN + O -> CN + OH { A = 3.910E+09 n = 1.580 E = 111.294 } NO57f: HCN + OH -> HOCN + H { A = 1.100E+06 n = 2.030 E = 55.940 } NO58f: HCN + OH -> HNCO + H { A = 4.400E+03 n = 2.260 E = 26.778 } NO59f: HCN + OH -> NH2 + CO { A = 1.600E+02 n = 2.560 E = 37.656 } NO60f: H + HCN + M34 -> H2CN + M34 { Ai = 3.300E+13 ni = 0.000 Ei= 0.000 A = 1.400E+26 n = -3.400 E = 7.950 fcc = 1.0 fctc = 0.0 } NO61f: H2CN + N -> N2 + T-CH2 { A = 6.000E+13 n = 0.000 E = 1.674 } NO62f: C + N2 -> CN + N { A = 6.300E+13 n = 0.000 E = 192.548 } NO63f: CH + N2 -> HCN + N { A = 3.120E+09 n = 0.880 E = 84.224 } NO64f: CH + N2 + M35 -> HCNN + M35 { Ai = 3.100E+12 ni = 0.150 Ei= 0.000 A = 1.300E+25 n = -3.160 E = 3.096 fcA = 3.330E-01 fctA = 2.350E+02 fcb = 6.670E-01 fctb = 2.117E+03 fcc = 1 fctc = 4.536E+03 } NO65f: T-CH2 + N2 -> HCN + NH { A = 1.000E+13 n = 0.000 E = 309.616 } NO66f: S-CH2 + N2 -> NH + HCN { A = 1.000E+11 n = 0.000 E = 271.960 } NO67f: C + NO -> CN + O { A = 1.900E+13 n = 0.000 E = 0.000 } NO68f: C + NO -> CO + N { A = 2.900E+13 n = 0.000 E = 0.000 } NO69f: CH + NO -> HCN + O { A = 4.100E+13 n = 0.000 E = 0.000 } NO70f: CH + NO -> H + NCO { A = 1.620E+13 n = 0.000 E = 0.000 } NO71f: CH + NO -> N + HCO { A = 2.460E+13 n = 0.000 E = 0.000 } NO72f: T-CH2 + NO -> H + HNCO { A = 3.100E+17 n = -1.380 E = 5.314 } NO73f: T-CH2 + NO -> OH + HCN { A = 2.900E+14 n = -0.690 E = 3.180 } NO74f: T-CH2 + NO -> H + HCNO { A = 3.800E+13 n = -0.360 E = 2.427 } NO75f: S-CH2 + NO -> H + HNCO { A = 3.100E+17 n = -1.380 E = 5.314 } NO76f: S-CH2 + NO -> OH + HCN { A = 2.900E+14 n = -0.690 E = 3.180 } NO77f: S-CH2 + NO -> H + HCNO { A = 3.800E+13 n = -0.360 E = 2.427 } NO78f: CH3 + NO -> HCN + H2O { A = 9.600E+13 n = 0.000 E = 120.499 } NO79f: CH3 + NO -> H2CN + OH { A = 1.000E+12 n = 0.000 E = 91.002 } NO80f: HCNN + O -> CO + H + N2 { A = 2.200E+13 n = 0.000 E = 0.000 } NO81f: HCNN + O -> HCN + NO { A = 2.000E+12 n = 0.000 E = 0.000 } NO82f: HCNN + O2 -> O + HCO + N2 { A = 1.200E+13 n = 0.000 E = 0.000 } NO83f: HCNN + OH -> H + HCO + N2 { A = 1.200E+13 n = 0.000 E = 0.000 } NO84f: HCNN + H -> T-CH2 + N2 { A = 1.000E+14 n = 0.000 E = 0.000 } NO85f: HNCO + O -> NH + CO2 { A = 9.800E+07 n = 1.410 E = 35.564 } NO86f: HNCO + O -> HNO + CO { A = 1.500E+08 n = 1.570 E = 184.096 } NO87f: HNCO + O -> NCO + OH { A = 2.200E+06 n = 2.110 E = 47.698 } NO88f: HNCO + H -> NH2 + CO { A = 2.250E+07 n = 1.700 E = 15.899 } NO89f: HNCO + H -> H2 + NCO { A = 1.050E+05 n = 2.500 E = 55.647 } NO90f: HNCO + OH -> NCO + H2O { A = 3.300E+07 n = 1.500 E = 15.062 } NO91f: HNCO + OH -> NH2 + CO2 { A = 3.300E+06 n = 1.500 E = 15.062 } NO92f: HNCO + M36 -> NH + CO + M36 { A = 1.180E+16 n = 0.000 E = 354.468 } NO93f: HCNO + H -> H + HNCO { A = 2.100E+15 n = -0.690 E = 11.924 } NO94f: HCNO + H -> OH + HCN { A = 2.700E+11 n = 0.180 E = 8.870 } NO95f: HCNO + H -> NH2 + CO { A = 1.700E+14 n = -0.750 E = 12.092 } NO96f: HOCN + H -> H + HNCO { A = 2.000E+07 n = 2.000 E = 8.368 } NO97f: HCCO + NO -> HCNO + CO { A = 9.000E+12 n = 0.000 E = 0.000 } NO98f: CH3 + N -> H2CN + H { A = 6.100E+14 n = -0.310 E = 1.213 } NO99f: CH3 + N -> HCN + H2 { A = 3.700E+12 n = 0.150 E = -0.377 } NO100f: NH3 + H -> NH2 + H2 { A = 5.400E+05 n = 2.400 E = 41.484 } NO101f: NH3 + OH -> NH2 + H2O { A = 5.000E+07 n = 1.600 E = 3.996 } NO102f: NH3 + O -> NH2 + OH { A = 9.400E+06 n = 1.940 E = 27.029 } NO103f: NH + CO2 -> HNO + CO { A = 1.000E+13 n = 0.000 E = 60.040 } NO104f: CN + NO2 -> NCO + NO { A = 6.160E+15 n = -0.752 E = 1.443 } NO105f: NCO + NO2 -> N2O + CO2 { A = 3.250E+12 n = 0.000 E = -2.950 } NO106f: N + CO2 -> NO + CO { A = 3.000E+12 n = 0.000 E = 47.279 } */ #================================================================# # # # Soot Formation # # # #================================================================# ###### H-Abstraction ###### # Tokmakov & Lin 1999/2002 # Rates indep of pressure # 1/6 of forward and full backward SOOT1f: Soot-CH + OH -> Soot-C + H2O { A = 6.72E+01 n = 3.33 E = 6.09 } SOOT1b: Soot-C + H2O -> Soot-CH + OH { A = 6.44E-01 n = 3.79 E = 27.96 } # Mebel & Lin 1997 # Rates indep of pressure # 1/6 of forward and full backward SOOT2f: Soot-CH + H -> Soot-C + H2 { A = 1.00E+08 n = 1.80 E = 68.42 } SOOT2b: Soot-C + H2 -> Soot-CH + H { A = 8.68E+04 n = 2.36 E = 25.46 } # Harding, Georgievskii & Klippenstein 2005 # High Pressure Limit # 1/6 of forward and full backward SOOT3f: Soot-CH -> Soot-C + H { A = 1.13E+16 n = -0.06 E = 476.05 } SOOT3b: Soot-C + H -> Soot-CH { A = 4.17E+13 n = 0.15 E = .00 } ###### C2H2-Addition ###### # Tokmakov & Lin 2004 # High pressure rates for A1- + C2H2 <=> A1C2H2 (x2) SOOT4: Soot-C + C2H2 -> Soot-CH noCheck { A = 2.52E+09 n = 1.10 E = 17.13 } ###### Oxidation ###### # Assume first reaction step is the limiting step: # Attack by O2 or OH # Kazakov, Wang & Frenklach 1995 SOOT5: Soot-C + O2 -> Soot-C + 2CO noCheck { A = 2.20E+12 n = .00 E = 31.38 } # Sarofim 1981 # Directly Coded in FlameMaster # From collision efficiency - 0.13 SOOT6 : Soot-CH + OH -> Soot-C + CO noCheck { A = 0.00E+00 n = .00 E = .00 } # **** Third Body ***** Let [M0] = 1.0 [OTHER]. Let [M1] = 0.00 [H2] + 0.00 [H2O] + 0.00 [CO2] + 0.63 [AR] + 1.0 [OTHER]. Let [M2] = 2.00 [H2] + 6.30 [H2O] + 1.75 [CO] + 3.60 [CO2] + 0.38 [AR] + 1.0 [OTHER]. Let [M3] = 2.00 [H2] + 12.00 [H2O] + 1.75 [CO] + 3.60 [CO2] + 0.70 [AR] + 1.0 [OTHER]. Let [M4] = 2.40 [H2] + 15.40 [H2O] + 1.75 [CO] + 3.60 [CO2] + 0.83 [AR] + 1.0 [OTHER]. Let [M5] = 0.75 [H2] + 11.89 [H2O] + 1.09 [CO] + 2.18 [CO2] + 0.50 [AR] + 0.85 [O2] + 1.0 [OTHER]. Let [M6] = 2.00 [H2] + 6.00 [H2O] + 1.75 [CO] + 3.60 [CO2] + 0.70 [AR] + 1.0 [OTHER]. Let [M7] = 2.00 [H2] + 12.00 [H2O] + 1.75 [CO] + 3.60 [CO2] + 0.70 [AR] + 1.0 [OTHER]. Let [M8] = 2.00 [H2] + 0.00 [H2O] + 1.75 [CO] + 3.60 [CO2] + 1.0 [OTHER]. Let [M9] = 2.00 [H2] + 6.00 [H2O] + 1.50 [CO] + 2.00 [CO2] + 0.70 [AR] + 2 [CH4] + 3 [C2H6] + 1.0 [OTHER]. /* let M28 = 2.00 [H2] + 6.00 [H2O] + 2.00 [CH4] + 1.50 [CO] + 2.00 [CO2] + 3.00 [C2H6] + 0.62 [AR] + 1.0 [OTHER]. let M29 = 2.00 [H2] + 6.00 [H2O] + 2.00 [CH4] + 1.50 [CO] + 2.00 [CO2] + 3.00 [C2H6] + 0.70 [AR] + 1.0 [OTHER]. let M30 = 2.00 [H2] + 6.00 [H2O] + 2.00 [CH4] + 1.50 [CO] + 2.00 [CO2] + 3.00 [C2H6] + 0.70 [AR] + 1.0 [OTHER]. let M31 = 2.00 [H2] + 6.00 [H2O] + 2.00 [CH4] + 1.50 [CO] + 2.00 [CO2] + 3.00 [C2H6] + 0.70 [AR] + 1.0 [OTHER]. let M32 = 2.00 [H2] + 6.00 [H2O] + 2.00 [CH4] + 1.50 [CO] + 2.00 [CO2] + 3.00 [C2H6] + 0.70 [AR] + 1.0 [OTHER]. let M33 = 2.00 [H2] + 6.00 [H2O] + 2.00 [CH4] + 1.50 [CO] + 2.00 [CO2] + 3.00 [C2H6] + 0.70 [AR] + 1.0 [OTHER]. let M34 = 2.00 [H2] + 6.00 [H2O] + 2.00 [CH4] + 1.50 [CO] + 2.00 [CO2] + 3.00 [C2H6] + 0.70 [AR] + 1.0 [OTHER]. let M35 = 2.00 [H2] + 6.00 [H2O] + 2.00 [CH4] + 1.50 [CO] + 2.00 [CO2] + 3.00 [C2H6] + 1.00 [AR] + 1.0 [OTHER]. let M36 = 2.00 [H2] + 6.00 [H2O] + 2.00 [CH4] + 1.50 [CO] + 2.00 [CO2] + 3.00 [C2H6] + 0.70 [AR] + 1.0 [OTHER]. */