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. #=========================================================================# # # # "An Improved H2/O2 Mechanism # # based on Recent Shock Tube/Laser Absorption Measurements" # # Hong, Davidson, Hanson, Combust. Flame (2011) # # # #=========================================================================# # Hydrogen/oxygen # --------------- 1f: H + O2 -> O + OH { A = 1.04E+14 n = .00 E = 63.96 } 2f: O + H2 -> H + OH { A = 3.82E+12 n = .00 E = 33.25 } 3f: O + H2 -> H + OH { A = 8.79E+14 n = .00 E = 80.21 } 4f: OH + H2 -> H + H2O { A = 2.17E+08 n = 1.52 E = 14.46 } 5f: OH + OH -> O + H2O { A = 3.57E+04 n = 2.40 E = -8.83 } # Davis et al. 2005 6f: 2 H + M1 -> H2 + M1 { A = 1.78E+18 n = -1.00 E = .00 } 7f: 2 H + H2 -> H2 + H2 { A = 9.00E+16 n = -0.60 E = .00 } 8f: 2 H + H2O -> H2 + H2O { A = 5.62E+19 n = -1.25 E = .00 } 9f: 2 H + CO2 -> H2 + CO2 { A = 5.50E+20 n = -2.00 E = .00 } 10f: O + H + M2 -> OH + M2 { A = 4.71E+18 n = -1.00 E = .00 } 11f: O + O + M3 -> O2 + M3 { A = 6.16E+15 n = -0.50 E = .00 } 12f: O + O + AR -> O2 + AR { A = 1.89E+13 n = .00 E = -7.48 } # All rates recombined into a single # Similar to Davis et al. 2005 # Collider efficiency evaluated at 1200K 13f: H + O2 + M4 -> HO2 + M4 { Ai= 5.59E+13 ni= 0.20 Ei= .00 A = 2.65E+19 n = -1.30 E = .00 fca = 0.3 fcta = 1.0E-10 fcb = 0.7 fctb = 1.0E+10 fcc = 1.0 fctc = 1.0E+10 } 14f: H2O + M5 -> OH + H + M5 { A = 6.06E+27 n = -3.31 E = 505.30 } 15f: H2O + H2O -> OH + H + H2O { A = 1.00E+26 n = -2.44 E = 502.75 } # Hydroperoxy radical # ------------------- 16f: HO2 + H -> H2 + O2 { A = 3.66E+06 n = 2.09 E = -6.07 } 17f: HO2 + H -> O + H2O { A = 1.45E+12 n = .00 E = .00 } 18f: HO2 + H -> OH + OH { A = 7.08E+13 n = .00 E = 1.26 } 19f: HO2 + O -> OH + O2 { A = 1.63E+13 n = .00 E = -1.86 } 20f: HO2 + OH -> H2O + O2 { A = 2.89E+13 n = .00 E = -2.09 } 21f: HO2 + HO2 -> H2O2 + O2 { A = 1.30E+11 n = .00 E = -6.71 } 22f: HO2 + HO2 -> H2O2 + O2 { A = 4.20E+14 n = .00 E = 50.12 } # Hydrogen peroxide # ----------------- # Low P from Hong et al. 2011 - refitted # Rest from Davis et al. 2005 23f: 2 OH + M6 -> H2O2 + M6 { A = 2.73E+19 n = -1.50 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 } 24f: H2O2 + H -> H2O + OH { A = 1.02E+13 n = .00 E = 14.97 } 25f: H2O2 + H -> HO2 + H2 { A = 1.21E+07 n = 2.00 E = 21.76 } 26f: H2O2 + O -> HO2 + OH { A = 8.43E+11 n = .00 E = 16.61 } 27f: H2O2 + OH -> HO2 + H2O { A = 1.74E+12 n = .00 E = 1.33 } 28f: H2O2 + OH -> HO2 + H2O { A = 7.59E+13 n = .00 E = 29.77 } #=========================================================================# # # # "An optimized kinetic model of H2/CO combustion" # # Davis, Joshi, Wang, and Egolfopoulos # # Proc. Comb. Inst. 30 (2005) 1283-1292 # # # #=========================================================================# # Carbon oxides # ------------- 30f: 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 } 31f: CO + OH -> CO2 + H { A = 8.00E+11 n = 0.14 E = 30.76 } 32f: CO + OH -> CO2 + H { A = 8.78E+10 n = 0.03 E = -0.07 } 33f: CO + O2 -> CO2 + O { A = 1.12E+12 n = .00 E = 199.58 } 34f: CO + HO2 -> CO2 + OH { A = 3.01E+13 n = .00 E = 96.23 } 35f: HCO + M8 -> CO + H + M8 { A = 1.87E+17 n = -1.00 E = 71.13 } 36f: HCO + H2O -> CO + H + H2O { A = 2.24E+18 n = -1.00 E = 71.13 } 37f: HCO + H -> CO + H2 { A = 1.20E+14 n = .00 E = .00 } 38f: HCO + O -> CO + OH { A = 3.00E+13 n = .00 E = .00 } 39f: HCO + OH -> CO + H2O { A = 3.02E+13 n = .00 E = .00 } 40f: HCO + O -> CO2 + H { A = 3.00E+13 n = .00 E = .00 } # New fit to experimental data # Colbergs & Friedrichs 2006 41f: HCO + O2 -> CO + HO2 { A = 5.31E+10 n = 0.69 E = -0.52 } #=========================================================================# # # # Chemistry of excited OH and CH states # # de Vries, Hall, Simmons, Rickard, Kalitan, Petersen 2007 # # (simplified) # # # #=========================================================================# # Excited OH* # ----------- E01f: S-OH -> OH { A = 1.40E+06 n = .00 E = .00 } E02f: S-OH + M0 -> OH + M0 { A = 2.17E+10 n = 0.50 E = 8.62 } E03f: S-OH + O2 -> OH + O2 { A = 2.10E+12 n = 0.50 E = -2.02 } E04f: O + H + M0 -> S-OH + M0 { A = 3.10E+14 n = .00 E = 41.84 } E05f: CH + O2 -> S-OH + CO { A = 3.24E+14 n = -0.40 E = 17.36 } # Excited CH* # ----------- E06f: S-CH -> CH { A = 1.86E+06 n = .00 E = .00 } E07f: S-CH + M0 -> CH + M0 { A = 4.00E+10 n = 0.50 E = .00 } E08f: S-CH + O2 -> CH + O2 { A = 2.48E+06 n = 2.14 E = -7.20 } E09f: C + H + M0 -> S-CH + M0 { A = 3.63E+13 n = .00 E = .00 } E10f: C2H + O -> S-CH + CO { A = 5.20E+11 n = .00 E = 10.88 } # Elsamra, Vranckx, Carl 2005 E11f: C2H + O2 -> S-CH + CO2 { A = 6.02E-04 n = 4.40 E = -9.56 } #=========================================================================# # # # 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 # # # #=========================================================================# # Carbon # ------ 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 } # Methylidyne # ----------- # Back to value before GRI opt # Dean, Davidson, Hanson 1991 G03f: CH + H -> C + H2 { A = 1.10E+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 } # Carbon oxides # ------------- 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 } # Methylene (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 -> CH3 + H { A = 5.00E+05 n = 2.00 E = 30.25 } # Alvarez, Moore, 1994 # Lee, Matsui, Chen, Wang 2012 # (revised branching ratios 0.58/0.20/0.22) G19f: T-CH2 + O2 -> HCO + OH { A = 9.57E+12 n = .00 E = 7.27 } G20f: T-CH2 + O2 -> CH2O + O { A = 3.30E+12 n = .00 E = 7.27 } G21f: T-CH2 + O2 -> CO2 + H2 { A = 3.63E+12 n = .00 E = 7.27 } 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: T-CH2 + T-CH2 -> C2H2 + H2 { A = 1.60E+15 n = .00 E = 49.97 } G27 : T-CH2 + T-CH2 -> C2H2 + 2 H { A = 2.00E+14 n = .00 E = 45.98 } # Methylene (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 + CO -> T-CH2 + CO { A = 9.00E+12 n = .00 E = .00 } G31f: S-CH2 + CO2 -> T-CH2 + CO2 { A = 7.00E+12 n = .00 E = .00 } G32f: S-CH2 + H2O -> T-CH2 + H2O { A = 3.00E+13 n = .00 E = .00 } G33f: S-CH2 + H -> CH + H2 { A = 3.00E+13 n = .00 E = .00 } G34f: S-CH2 + O -> CO + H2 { A = 1.50E+13 n = .00 E = .00 } G35f: S-CH2 + O -> HCO + H { A = 1.50E+13 n = .00 E = .00 } G36f: S-CH2 + H2 -> CH3 + H { A = 7.00E+13 n = .00 E = .00 } G37 : S-CH2 + O2 -> CO + OH + H { A = 2.80E+13 n = .00 E = .00 } G38f: S-CH2 + O2 -> CO + H2O { A = 1.20E+13 n = .00 E = .00 } G39f: 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 } G40f: S-CH2 + OH -> CH2O + H { A = 3.00E+13 n = .00 E = .00 } G41 : S-CH2 + H2O -> CH2O + H2 { A = 6.82E+10 n = .25 E = -3.91 } G42f: S-CH2 + CO2 -> CH2O + CO { A = 1.40E+13 n = .00 E = .00 } # Formaldehyde # ------------ # Dames & Golden 2013 G43f: CH2OH + M9 -> CH2O + H + M9 { A = 3.50E+21 n = -1.99 E = 100.41 Ai= 7.37E+10 ni= 0.81 Ei= 165.61 fcA = 0.156 fctA = 900 fcb = 0.844 fctb = 1 fcc = 1.0 fctc = 3315 } G44f: CH3O + M9 -> CH2O + H + M9 { A = 6.02E+16 n = -0.55 E = 75.41 Ai= 1.13E+10 ni= 1.21 Ei= 100.77 fcA = 0.659 fctA = 28 fcb = 0.341 fctb = 1000 fcc = 1.0 fctc = 2339 } 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 } # Methyl radical # -------------- # Golden 2013 # Baulch et al.; Troe Ushakov G51f: CH3 + H + M9 -> CH4 + M9 { A = 2.79E+34 n = -5.10 E = 11.65 Ai= 4.36E+13 ni= 0.19 Ei= .00 fcA = 0.37 fctA = 61 fcb = 0.63 fctb = 3315 fcc = 1.0 fctc = 1e10 } # Harding, Klippenstein, Georgievskii 2005 # Reactions lumped - Products changed G52f: CH3 + O -> CH2O + H { A = 5.54E+13 n = 0.05 E = -0.57 } 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 } G56f: CH3 + OH -> S-CH2 + H2O { A = 6.44E+17 n = -1.34 E = 5.93 } G57: CH3 + OH -> CH2O + H2 { A = 8.00E+09 n = .00 E = -7.34 } # 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 } # Jasper, Klippensteion, Harding 2009 G65f: CH3 + HO2 -> CH3O + OH { A = 1.00E+12 n = 0.29 E = -2.87 } G66f: CH3 + HO2 -> CH4 + O2 { A = 1.19E+05 n = 2.23 E = -12.65 } G67f: CH3 + H2O2 -> CH4 + HO2 { A = 2.45E+04 n = 2.47 E = 21.67 } G68f: CH3 + HCO -> CH4 + CO { A = 2.65E+13 n = .00 E = .00 } G69f: CH3 + CH2O -> CH4 + HCO { A = 3.32E+03 n = 2.81 E = 24.52 } G70f: CH3 + C -> C2H2 + H { A = 5.00E+13 n = .00 E = .00 } G71f: CH3 + CH -> C2H3 + H { A = 3.00E+13 n = .00 E = .00 } 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: CH3 + CH3 -> C2H5 + H { A = 6.84E+12 n = 0.10 E = 44.35 } # Methoxy radical # --------------- 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 -> CH3 + OH { A = 1.50E+12 n = 0.50 E = -0.46 } G77f: CH3O + H -> S-CH2 + H2O { A = 2.62E+14 n = -0.23 E = 4.48 } G78f: CH3O + H -> CH2O + H2 { A = 2.00E+13 n = .00 E = .00 } G79f: CH3O + O -> CH2O + OH { A = 1.00E+13 n = .00 E = .00 } G80f: CH3O + OH -> CH2O + H2O { A = 5.00E+12 n = .00 E = .00 } # Baulch et al. 2005 G81f: CH3O + O2 -> CH2O + HO2 { A = 6.17E+10 n = .00 E = 7.32 } G82f: CH2OH + H + M9 -> CH3OH + M9 { A = 4.36E+31 n = -4.65 E = 21.26 Ai= 1.06E+12 ni= 0.50 Ei= 0.36 fcA = 0.400 fctA = 100 fcb = 0.600 fctb = 9000 fcc = 1.0 fctc = 10000 } G83f: CH2OH + H -> CH3 + OH { A = 1.65E+11 n = 0.65 E = -1.19 } G84f: CH2OH + H -> S-CH2 + H2O { A = 3.28E+13 n = -0.09 E = 2.55 } G85f: CH2OH + H -> CH2O + H2 { A = 2.00E+13 n = .00 E = .00 } G86f: CH2OH + O -> CH2O + OH { A = 1.00E+13 n = .00 E = .00 } G87f: CH2OH + OH -> CH2O + H2O { A = 5.00E+12 n = .00 E = .00 } G88f: CH2OH + O2 -> CH2O + HO2 { A = 1.80E+13 n = .00 E = 3.77 } G89f: CH3O + H -> CH2OH + H { A = 4.15E+07 n = 1.63 E = 8.05 } # Methane # ------- 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 } G94f: CH4 + T-CH2 -> CH3 + CH3 { A = 2.46E+06 n = 2.00 E = 34.60 } G95f: CH4 + S-CH2 -> CH3 + CH3 { A = 1.60E+13 n = .00 E = -2.39 } G93f: CH4 + CH -> C2H4 + H { A = 6.00E+13 n = .00 E = .00 } # Methanol # -------- G96f: CH3OH + H -> CH2OH + H2 { A = 1.70E+07 n = 2.10 E = 20.38 } G97f: CH3OH + O -> CH2OH + OH { A = 3.88E+05 n = 2.50 E = 12.97 } G98f: CH3OH + OH -> CH2OH + H2O { A = 1.44E+06 n = 2.00 E = -3.52 } G99f: CH3OH + CH3 -> CH2OH + CH4 { A = 3.00E+07 n = 1.50 E = 41.59 } G100f: CH3OH + H -> CH3O + H2 { A = 4.20E+06 n = 2.10 E = 20.38 } G101f: CH3OH + O -> CH3O + OH { A = 1.30E+05 n = 2.50 E = 20.92 } G102f: CH3OH + OH -> CH3O + H2O { A = 6.30E+06 n = 2.00 E = 6.28 } G103f: CH3OH + CH3 -> CH3O + CH4 { A = 1.00E+07 n = 1.50 E = 41.59 } # Acetyl radical # -------------- 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 -> HCCO + H { A = 2.00E+13 n = .00 E = .00 } G107f: C2H + O2 -> HCO + CO { A = 1.00E+13 n = .00 E = -3.16 } # Carl, Vereecken & Peeters 2007 G108f: C2H + H2 -> C2H2 + H { A = 2.36E+05 n = 2.57 E = 1.08 } # Ketenyl radical # --------------- # Revised based on Carl, Vereecken & Peeters 2007 G109f: HCCO + H -> S-CH2 + CO { A = 1.00E+14 n = .00 E = .00 } G110f: HCCO + CH -> C2H2 + CO { A = 5.00E+13 n = .00 E = .00 } G111f: HCCO + T-CH2 -> C2H3 + CO { A = 3.00E+13 n = .00 E = .00 } G112f: HCCO + CH3 -> C2H4 + CO { A = 5.00E+13 n = .00 E = .00 } G113 : HCCO + HCCO -> C2H2 + 2 CO { A = 1.00E+13 n = .00 E = .00 } G114 : HCCO + O -> H + 2 CO { A = 7.22E+13 n = .00 E = .00 } # Mai, Raghunath, Le, Huynh, Nam, Lin 2014 G115f: HCCO + OH -> CH2O + CO { A = 1.88E+16 n = -0.59 E = 0.61 } G116f: HCCO + OH -> T-CH2 + CO2 { A = 8.97E+04 n = 2.09 E = -9.19 } # Klippenstein, Miller, Harding 2002 G117 : HCCO + O2 -> CO2 + CO + H { A = 4.78E+12 n = -0.14 E = 4.81 } G118 : HCCO + O2 -> 2CO + OH { A = 1.91E+11 n = -0.02 E = 4.28 } # Acetylene # --------- # Miller & Klippenstein 2004 # Refitted TROE form G119f: 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 = 0.751 fctA = 12.1 fcb = 0.249 fctb = 10000 fcc = 1.0 fctc = 5493 } # Nguyen, Vereecken, Peeters 2006 - Total rate # Rajak & Maiti 2010 - Branching ratios G120f: C2H2 + O -> HCCO + H { A = 2.96E+09 n = 1.28 E = 10.34 } G121f: C2H2 + O -> T-CH2 + CO { A = 7.40E+08 n = 1.28 E = 10.34 } # Tsang & Hampson 1986 # Modified for Collision Limit G122f: C2H + OH -> C2H2 + O { A = 1.81E+13 n = .00 E = .00 } # Senosiain, Klippenstein & Miller 2005 # HCCOH lumped into CH2CO G123f: C2H2 + OH -> C2H + H2O { A = 2.63E+06 n = 2.14 E = 71.38 } G124f: C2H2 + OH -> CH2CO + H { A = 2.10E+01 n = 3.22 E = -1.76 } G125f: C2H2 + OH -> CH3 + CO { A = 1.28E+09 n = 0.73 E = 10.79 } # Laskin & Wang 1999 G126f: C2H2 + M9 -> H2C2 + M9 { A = 2.45E+15 n = -0.64 E = 207.94 } G127f: H2C2 + O2 -> 2 HCO { A = 1.00E+13 n = .00 E = .00 } # Ketene # ------ # Updated by Eiteneer & Frenklach 2003 G128f: CH2CO + H -> HCCO + H2 { A = 5.00E+13 n = .00 E = 33.47 } G129f: CH2CO + O -> HCCO + OH { A = 1.00E+13 n = .00 E = 33.47 } G130f: CH2CO + OH -> HCCO + H2O { A = 7.50E+12 n = .00 E = 8.37 } G131f: CH2CO + T-CH2 -> HCCO + CH3 { A = 3.60E+13 n = .00 E = 46.02 } # Woods & Haynes 1994 G132f: CH2CO + CH3 -> HCCO + CH4 { A = 7.50E+12 n = .00 E = 54.39 } G133f: CH2CO + CH3 -> C2H5 + CO { A = 9.00E+10 n = .00 E = .00 } # Senosiain, Klippenstein & Miller 2006 G134f: CH2CO + H -> CH3 + CO { A = 7.77E+08 n = 1.45 E = 11.63 } # Lee & Bozzelli 2002 G135f: CH2CO + OH -> CH2OH + CO { A = 5.00E+12 n = .00 E = .00 } G136f: CH2CO + T-CH2 -> C2H4 + CO { A = 1.00E+12 n = .00 E = .00 } G137f: CH2CO + O -> T-CH2 + CO2 { A = 1.75E+12 n = .00 E = 5.65 } # Vinyl radical # ------------- G138f: 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 } G139f: C2H3 + H -> C2H2 + H2 { A = 3.00E+13 n = .00 E = .00 } # Harding, Klippenstein & Georgievskii 2005 G140f: C2H3 + O -> CH2CHO { A = 1.03E+13 n = 0.21 E = -1.79 } G141f: C2H3 + OH -> C2H2 + H2O { A = 5.00E+12 n = .00 E = .00 } G142f: C2H3 + O2 -> C2H2 + HO2 { A = 1.34E+06 n = 1.61 E = -1.61 } # Stoliarov et al. 2002 G143f: C2H3 + CH3 -> C2H2 + CH4 { A = 9.03E+12 n = .00 E = -3.20 } G144f: C2H3 + O2 -> CH2CHO + O { A = 3.03E+11 n = 0.29 E = 0.05 } G145f: C2H3 + O2 -> HCO + CH2O { A = 4.58E+16 n = -1.39 E = 4.25 } G146f: C2H3 + H2O2 -> C2H4 + HO2 { A = 1.21E+10 n = .00 E = -2.49 } G147f: C2H3 + HCO -> C2H4 + CO { A = 9.00E+13 n = .00 E = .00 } # CH2CHO # ------ # Senosiain, Klippenstein & Miller 2006 G148f: CH2CHO -> CH2CO + H { A = 1.32E+34 n = -6.57 E = 202.45 } G149f: CH2CHO -> CH3 + CO { A = 6.51E+34 n = -6.87 E = 197.46 } # Same as for C2H5 + O G150f: CH2CHO + O -> CH2O + HCO { A = 3.17E+13 n = 0.03 E = -1.65 } G151 : CH2CHO + O2 -> CH2O + CO + OH { A = 1.81E+10 n = .00 E = 0.00 } G152 : CH2CHO + O2 -> 2 HCO + OH { A = 2.35E+10 n = .00 E = 0.00 } G153f: CH2CHO + H -> CH2CO + H2 { A = 1.10E+13 n = .00 E = 0.00 } G154f: CH2CHO + OH -> CH2CO + H2O { A = 1.20E+13 n = .00 E = 0.00 } G155f: CH2CHO + H -> CH3 + HCO { A = 2.20E+13 n = .00 E = 0.00 } G156f: CH2CHO + OH -> CH2OH + HCO { A = 3.01E+13 n = .00 E = 0.00 } G157f: CH2CHO + CH3 -> C2H5 + HCO { A = 4.90E+14 n = -0.50 E = .00 } # Acetaldehyde # ------------ # Baulch et al. 2005 - HPL - Backward # Modified for collision limit G158f: CH3 + HCO -> CH3CHO { A = 5.00E+13 n = .00 E = .00 } G159f: CH3CHO + O -> CH2CHO + OH { A = 2.92E+12 n = .00 E = 7.57 } G160f: CH3CHO + H -> CH2CHO + H2 { A = 2.05E+09 n = 1.16 E = 10.06 } G161 : CH3CHO + H -> CH3 + CO + H2 { A = 2.05E+09 n = 1.16 E = 10.06 } G162 : CH3CHO + O -> CH3 + CO + OH { A = 2.92E+12 n = .00 E = 7.57 } G163 : CH3CHO + OH -> CH3 + CO + H2O { A = 2.34E+10 n = .73 E = -4.66 } G164 : CH3CHO + O2 -> CH3 + CO + HO2 { A = 3.01E+13 n = .00 E = 163.80 } G165 : CH3CHO + HO2 -> CH3 + CO + H2O2 { A = 3.01E+12 n = .00 E = 49.89 } G166 : CH3CHO + CH3 -> CH3 + CO + CH4 { A = 2.72E+06 n = 1.77 E = 24.77 } # Ethylene # -------- # Ren, Davidson, Hanson 2012 G167f: C2H4 + M9 -> H2C2 + H2 + M9 { A = 2.60E+16 n = .00 E = 283.76 } # Miller & Klippenstein 2004 # Refitted TROE form G168f: 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 = 0.74 fctA = 361.7 fcb = 0.26 fctb = 10000 fcc = 1.0 fctc = 9096 } # Huynh, Panasewicz, Ratkiewicz, Truong 2007 # Closer to the recommendation of Baulch et al. 2005 G169f: C2H4 + H -> C2H3 + H2 { A = 1.27E+05 n = 2.75 E = 48.74 } # Nguyen, Vereecken, Hou, Nguyen, Peeters 2005 G170f: C2H4 + O -> CH2CHO + H { A = 7.66E+09 n = 0.88 E = 4.77 } G171f: C2H4 + O -> T-CH2 + CH2O { A = 7.15E+04 n = 2.47 E = 3.89 } G172f: C2H4 + O -> CH3 + HCO { A = 3.89E+08 n = 1.36 E = 3.71 } # Vasu, Hong, Davidson, Hanson, Golden 2010 G173f: C2H4 + OH -> C2H3 + H2O { A = 2.23E+04 n = 2.75 E = 9.27 } # Wang 2001 G174f: C2H4 + O2 -> C2H3 + HO2 { A = 4.22E+13 n = .00 E = 259.83 } G175 : C2H4 + O2 -> CH3 + CO2 + H { A = 4.90E+12 n = 0.42 E = 317.15 } # Miller & Klippenstein 2013 G176f: C2H4 + CH3 -> C2H3 + CH4 { A = 2.06E-01 n = 3.94 E = 51.98 } G177f: 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 } # Ethyl radical # ------------- G178f: 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 } G179f: C2H5 + H -> C2H4 + H2 { A = 2.00E+12 n = .00 E = .00 } # Miller, Klippenstein & Robertson 2000 G180f: C2H5 + O2 -> C2H4 + HO2 { A = 1.92E+07 n = 1.02 E = -8.51 } # Zhu, Xu & Lin 2004 G181f: C2H5 + CH3 -> C2H4 + CH4 { A = 1.18E+04 n = 2.45 E = 12.22 } # Harding, Klippenstein & Georgievskii 2005 G182f: C2H5 + O -> CH3 + CH2O { A = 3.17E+13 n = 0.03 E = -1.65 } # Ludwig et al. 2006 G183f: C2H5 + HO2 -> C2H5O + OH { A = 3.10E+13 n = .00 E = .00 } G184f: C2H5 + HCO -> C2H6 + CO { A = 1.20E+14 n = .00 E = .00 } G185f: C2H5 + HO2 -> C2H6 + O2 { A = 3.00E+11 n = .00 E = .00 } G186f: C2H5 + HO2 -> C2H4 + H2O2 { A = 3.00E+11 n = .00 E = .00 } # Ethoxy radical # -------------- # Dames 2014 G187f: C2H5O + M9 -> CH3 + CH2O + M9 { A = 4.70E+25 n = -3.00 E = 69.17 Ai= 6.31E+10 ni= 0.93 Ei= 71.54 fcA = 0.574 fctA = 0.3 fcb = 0.426 fctb = 2046 fcc = 1.0 fctc = 1e5 } # Baulch et al. 2005 G188f: C2H5O + O2 -> CH3CHO + HO2 { A = 2.29E+10 n = .00 E = 3.66 } # Ethane # ------ # Oehlschlaeger et al. 2005 G189f: 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 G190f: C2H6 + H -> C2H5 + H2 { A = 1.70E+05 n = 2.70 E = 24.02 } # Huynh, Zhang, Truong 2008 G191f: C2H6 + O -> C2H5 + OH { A = 3.17E+01 n = 3.80 E = 13.10 } # Krasnoperov & Michael 2004 G192f: C2H6 + OH -> C2H5 + H2O { A = 1.61E+06 n = 2.22 E = 3.10 } # Carstensen & Dean 2005 G193f: C2H6 + HO2 -> C2H5 + H2O2 { A = 2.61E+02 n = 3.37 E = 66.58 } G194f: C2H6 + S-CH2 -> C2H5 + CH3 { A = 4.00E+13 n = .00 E = -2.30 } # Peukert, Labbe, Sivaramakrishnan, Michael 2013 G195f: C2H6 + CH3 -> C2H5 + CH4 { A = 3.45E+01 n = 3.44 E = 43.47 } # Propyl radicals # --------------- # Curran 2006 - HPL G196f: 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 } G197f: 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 } G198f: N-C3H7 + H -> C2H5 + CH3 { A = 3.70E+24 n = -2.92 E = 52.32 } G199f: I-C3H7 + H -> C2H5 + CH3 { A = 1.40E+28 n = -3.94 E = 66.59 } G200f: N-C3H7 + H -> C3H6 + H2 { A = 1.80E+12 n = .00 E = .00 } G201f: I-C3H7 + H -> C3H6 + H2 { A = 3.20E+12 n = .00 E = .00 } G202f: N-C3H7 + O -> C2H5 + CH2O { A = 9.60E+13 n = .00 E = .00 } G203f: I-C3H7 + O -> CH3CHO + CH3 { A = 9.60E+13 n = .00 E = .00 } G204f: N-C3H7 + OH -> C3H6 + H2O { A = 2.41E+13 n = .00 E = .00 } G205f: I-C3H7 + OH -> C3H6 + H2O { A = 2.41E+13 n = .00 E = .00 } # DeSain, Miller, Klippenstein & Taatjes 2003 G206f: N-C3H7 + O2 -> C3H6 + HO2 { A = 3.70E+16 n = -1.63 E = 14.30 } G207f: 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 G208f: N-C3H7 + CH3 -> C3H6 + CH4 { A = 3.31E+12 n = .00 E = -3.22 } # Propane # ------- # From Tsang 1988 G209f: 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 } G210f: 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 } # Oehlschlaeger et al. 2005 G211f: 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 } # Carstensen & Dean 2009 G212f: C3H8 + H -> N-C3H7 + H2 { A = 9.36E+07 n = 1.97 E = 34.31 } G213f: C3H8 + H -> I-C3H7 + H2 { A = 7.60E+07 n = 1.86 E = 23.43 } G214f: C3H8 + O -> N-C3H7 + OH { A = 1.90E+05 n = 2.68 E = 15.55 } G215f: C3H8 + O -> I-C3H7 + OH { A = 4.76E+04 n = 2.71 E = 08.81 } # Sivaramkrishnan, Srinivasan, Su, Michael 2009 G216f: C3H8 + OH -> N-C3H7 + H2O { A = 5.15E+03 n = 2.94 E = -1.75 } G217f: C3H8 + OH -> I-C3H7 + H2O { A = 1.81E+05 n = 2.44 E = -2.24 } G218f: C3H8 + CH3 -> N-C3H7 + CH4 { A = 9.03E-01 n = 3.65 E = 29.93 } G219f: C3H8 + CH3 -> I-C3H7 + CH4 { A = 1.51E+00 n = 3.46 E = 29.93 } G220f: C3H8 + HO2 -> N-C3H7 + H2O2 { A = 4.76E+04 n = 2.55 E = 69.00 } G221f: C3H8 + HO2 -> I-C3H7 + H2O2 { A = 9.63E+03 n = 2.60 E = 58.20 } #=========================================================================# # # # "Experimental and Modeling Study of Shock-Tube Oxidation of Acetylene" # # B. Eiteneer and M. Frenklach # # Int. J. Chem. Kinet. 35, 391:414 (2003) # # # #=========================================================================# # Propynylidene # ------------- R005f: C3H2 + O -> C3H2O { A = 1.36E+14 n = .00 E = .00 } R006f: C3H2 + OH -> C2H2 + HCO { A = 1.00E+13 n = .00 E = .00 } R007f: C3H2 + O2 -> HCCO + CO + H { A = 1.25E+11 n = .00 E = 4.18 } R008f: C3H2 + CH -> C4H2 + H { A = 5.00E+13 n = .00 E = .00 } R009f: C3H2 + T-CH2 -> N-C4H3 + H { A = 5.00E+13 n = .00 E = .00 } R010f: C3H2 + CH3 -> C4H4 + H { A = 5.00E+12 n = .00 E = .00 } R011f: C3H2 + HCCO -> N-C4H3 + CO { A = 1.00E+13 n = .00 E = .00 } # Propynal # -------- # Estimated R012f: C2H + HCO -> C3H2O { A = 5.00E+13 n = .00 E = .00 } # From P-C3H4 + H R013f: C3H2O + H -> C2H2 + HCO { A = 3.46E+12 n = 0.44 E = 22.86 } # Taken from CH3CHO R014 : C3H2O + H -> C2H + CO + H2 { A = 2.05E+09 n = 1.16 E = 10.06 } R015 : C3H2O + O -> C2H + CO + OH { A = 2.92E+12 n = .00 E = 7.57 } R016 : C3H2O + O2 -> C2H + CO + HO2 { A = 3.01E+13 n = .00 E = 163.80 } R017 : C3H2O + OH -> C2H + CO + H2O { A = 2.34E+10 n = .73 E = -4.66 } R018 : C3H2O + HO2 -> C2H + CO + H2O2 { A = 3.01E+12 n = .00 E = 49.89 } R019 : C3H2O + CH3 -> C2H + CO + CH4 { A = 2.72E+06 n = 1.77 E = 24.77 } # Propargyl radical # ----------------- R020f: C2H2 + HCCO -> C3H3 + CO { A = 1.00E+11 n = .00 E = 12.55 } # Tsang & Hampson 1986 R021f: C2H + CH3 -> C3H3 + H { A = 2.41E+13 n = .00 E = .00 } # Polino, Klippenstein, Harding, Georgievskii 2013 R022f: C2H2 + S-CH2 -> C3H3 + H { A = 3.97E+15 n = -0.57 E = -0.02 } # 2x rate for C2H3+H R023f: 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) R024f: C3H3 + H -> C3H2 + H2 { A = 1.10E+10 n = 1.13 E = 58.28 } # Adapted from C2H2 + OH R025f: C3H3 + OH -> C2H3CHO { A = 2.10E+01 n = 3.22 E = -1.76 } R026f: C3H3 + OH -> C2H4 + CO { A = 1.28E+09 n = 0.73 E = 10.79 } # 1/2 rate for C2H4+OH R027f: C3H3 + OH -> C3H2 + H2O { A = 1.13E+05 n = 2.28 E = 10.32 } # Lee, Nam & Choi 2006 # Kwon, Nam, Youn, Joo, Lee, & Choi 2006 # Slagle, Gmurczyk, Batt & Gutman 1991 R029f: C3H3 + O -> C3H2O + H { A = 1.38E+14 n = .00 E = .00 } # Hahn, Klippenstein, Miller 2001 R030f: C3H3 + O2 -> CH2CO + HCO { A = 1.70E+05 n = 1.70 E = 6.28 } R031 : C3H3 + HO2 -> C2H3 + CO + OH { A = 8.00E+11 n = .00 E = .00 } # Wang 2001 R032f: C3H3 + HO2 -> A-C3H4 + O2 { A = 3.00E+11 n = .00 E = .00 } R033f: C3H3 + HO2 -> P-C3H4 + O2 { A = 3.00E+11 n = .00 E = .00 } R034f: P-C3H4 + O2 -> CH3 + HCO + CO { A = 4.00E+14 n = .00 E = 175.43 } R035f: C3H3 + HCO -> A-C3H4 + CO { A = 2.50E+13 n = .00 E = .00 } R036f: C3H3 + HCO -> P-C3H4 + CO { A = 2.50E+13 n = .00 E = .00 } R037f: C3H3 + CH -> I-C4H3 + H { A = 5.00E+13 n = .00 E = .00 } # Miller, Melius 1992 R038f: C3H3 + T-CH2 -> C4H4 + H { A = 5.00E+13 n = .00 E = .00 } # Propyne & Allene # ---------------- # Thiesemann, Clifford, Taatjes, Klippenstein 2001 # Zhang, Maksyutenko, Kaiser 2012 R200f: C2H4 + CH -> A-C3H4 + H { A = 9.98E+14 n = -0.31 E = .00 } # Miller & Klippenstein 2003 (1bar) R039f: A-C3H4 -> P-C3H4 { A = 7.76E+39 n = -7.80 E = 328.22 } # Giri, Fernandes, Bentz, Hippler, Olzmann 2011 R040f: P-C3H4 + M0 -> C3H3 + H + M0 { A = 2.15E+43 n = -6.81 E = 420.61 } R041f: A-C3H4 + M0 -> C3H3 + H + M0 { A = 2.15E+43 n = -6.81 E = 420.61 } # Miller, Senosiain, Klippenstein, Georgievskii 2008 # Refitted 800K-2500K - 1bar R042f: A-C3H4 + H -> C2H2 + CH3 { A = 8.95E+13 n = -0.02 E = 47.07 } # Sheen, Rosado-Reyes, Tsang 2013 R043f: C2H2 + CH3 -> P-C3H4 + H { A = 1.48E+11 n = 0.60 E = 59.86 } R044f: P-C3H4 + H -> A-C3H4 + H { A = 1.58E+18 n = -1.00 E = 50.72 } # Miller, Senosiain, Klippenstein, Georgievskii 2008 # P=1bar R045f: A-C3H4 + H -> A-C3H5 { A = 2.01E+49 n =-10.77 E = 82.10 } R046f: A-C3H4 + H -> T-C3H5 { A = 6.70E+42 n =-12.46 E = 68.45 } R047f: P-C3H4 + H -> T-C3H5 { A = 8.83E+52 n =-12.36 E = 68.81 } R048f: P-C3H4 + H -> S-C3H5 { A = 1.53E+49 n =-11.97 E = 59.18 } # 1/2 the rate for C2H6 R049f: P-C3H4 + H -> C3H3 + H2 { A = 8.50E+04 n = 2.70 E = 24.02 } R050f: P-C3H4 + O -> C3H3 + OH { A = 1.59E+01 n = 3.80 E = 13.10 } R051f: P-C3H4 + OH -> C3H3 + H2O { A = 8.05E+05 n = 2.22 E = 3.10 } R052f: P-C3H4 + CH3 -> C3H3 + CH4 { A = 1.73E+01 n = 3.44 E = 43.47 } R053f: P-C3H4 + HO2 -> C3H3 + H2O2 { A = 1.30E+02 n = 3.37 E = 66.58 } # Same as for C2H4 R054f: A-C3H4 + H -> C3H3 + H2 { A = 1.33E+06 n = 2.53 E = 51.21 } R055f: A-C3H4 + OH -> C3H3 + H2O { A = 1.31E-01 n = 4.20 E = -3.60 } R056f: A-C3H4 + CH3 -> C3H3 + CH4 { A = 2.27E+05 n = 2.00 E = 38.49 } R057f: A-C3H4 + HO2 -> C3H3 + H2O2 { A = 9.76E+10 n = 0.12 E = 97.78 } # Nguyen, Peeters & Vereecken 2006 # Total rate assigned R058f: A-C3H4 + O -> CH2CO + T-CH2 { A = 9.63E+06 n = 2.05 E = 0.75 } # Adapted from C2H2+O # Zhao, Wu, Zhao et al. 2009 - Products R059f: P-C3H4 + O -> C2H4 + CO { A = 3.70E+09 n = 1.28 E = 10.34 } # From C2H2 + OH R060f: P-C3H4 + OH -> CH2CO + CH3 { A = 2.10E+01 n = 3.22 E = -1.76 } R061f: P-C3H4 + OH -> C2H5 + CO { A = 1.28E+09 n = 0.73 E = 10.79 } R062f: A-C3H4 + C2H -> C2H2 + C3H3 { A = 1.00E+13 n = .00 E = .00 } R063f: P-C3H4 + C2H -> C2H2 + C3H3 { A = 1.00E+13 n = .00 E = .00 } # Liu, Maluc, Jonah 1988 R064f: A-C3H4 + OH -> CH2CO + CH3 { A = 4.03E+12 n = .00 E = -0.83 } # Propenal # -------- R065f: C2H3 + HCO -> C2H3CHO { A = 1.80E+13 n = .00 E = .00 } # Baulch et al. 2005 - adapted from CH3CHO R066 : C2H3CHO + H -> C2H3 + CO + H2 { A = 4.09E+09 n = 1.16 E = 10.06 } R067 : C2H3CHO + O -> C2H3 + CO + OH { A = 5.84E+12 n = .00 E = 7.57 } R068 : C2H3CHO + OH -> C2H3 + CO + H2O { A = 2.89E+08 n = 1.35 E = -6.58 } R069 : C2H3CHO + HO2 -> C2H3 + CO + H2O2 { A = 4.09E+04 n = 2.50 E = 42.69 } R070 : C2H3CHO + CH3 -> C2H3 + CO + CH4 { A = 3.49E-08 n = 6.21 E = 6.82 } # Allyl radicals # -------------- # Miller, Senosiain, Klippenstein, Georgievskii 2008 # Refitted 800K-2500K - P=1bar R071f: C2H2 + CH3 -> S-C3H5 { A = 7.45E+43 n =-10.13 E = 77.50 } # Davis, Law, Wang 1999 (1bar) R072f: A-C3H5 -> T-C3H5 { A = 7.06E+56 n =-14.08 E = 317.43 } R073f: A-C3H5 -> S-C3H5 { A = 5.00E+51 n =-13.02 E = 306.69 } R074f: T-C3H5 -> S-C3H5 { A = 1.50E+48 n =-12.71 E = 225.52 } # Klippenstein, Harding, Georgievskii, Miller 2008 # Fitted 400K-2500K R075f: A-C3H5 + H -> A-C3H4 + H2 { A = 9.56E+03 n = 2.80 E = 13.77 } # Tsang 1991 R076f: A-C3H5 + OH -> A-C3H4 + H2O { A = 6.03E+12 n = .00 E = .00 } R077f: A-C3H5 + CH3 -> A-C3H4 + CH4 { A = 3.01E+12 n = -0.32 E = -0.55 } R078f: A-C3H5 + C2H3 -> A-C3H4 + C2H4 { A = 2.41E+12 n = .00 E = .00 } R079f: A-C3H5 + C2H5 -> A-C3H4 + C2H6 { A = 9.64E+11 n = .00 E = -0.55 } # Lee & Bozzelli 2005 R081f: A-C3H5 + O2 -> A-C3H4 + HO2 { A = 2.06E+04 n = 2.19 E = 73.60 } R082f: A-C3H5 + O2 -> C2H3CHO + OH { A = 3.36E+05 n = 1.81 E = 80.29 } R083 : A-C3H5 + O2 -> C2H2 + CH2O + OH { A = 9.71E+20 n = -2.70 E = 104.52 } R084f: A-C3H5 + O2 -> CH2CHO + CH2O { A = 3.08E+09 n = 0.37 E = 70.75 } # Estimated from C2H5+O # Park, lee, Choi 2003 - Products R085f: A-C3H5 + O -> C2H3CHO + H { A = 3.17E+13 n = 0.03 E = -1.65 } R086 : A-C3H5 + OH -> C2H3CHO + H2 { A = 4.20E+32 n = -5.16 E = 126.05 } R087f: A-C3H5 + HCO -> C3H6 + CO { A = 6.00E+13 n = .00 E = .00 } R088f: A-C3H5 + HO2 -> C3H6 + O2 { A = 2.66E+12 n = .00 E = .00 } # From A1CH2+HO2 R089f: A-C3H5 + HO2 -> C3H5O + OH { A = 1.19E+09 n = 1.03 E = -9.41 } R090f: T-C3H5 + H -> P-C3H4 + H2 { A = 3.34E+12 n = .00 E = .00 } R091f: T-C3H5 + O -> CH3 + CH2CO { A = 6.00E+13 n = .00 E = .00 } R092 : T-C3H5 + OH -> CH3 + CH2CO + H { A = 5.00E+12 n = .00 E = .00 } R093 : T-C3H5 + HO2 -> CH3 + CH2CO + OH { A = 2.00E+13 n = .00 E = .00 } R094f: T-C3H5 + HCO -> C3H6 + CO { A = 9.00E+13 n = .00 E = .00 } R095f: T-C3H5 + CH3 -> P-C3H4 + CH4 { A = 1.00E+11 n = .00 E = .00 } R096f: S-C3H5 + H -> P-C3H4 + H2 { A = 3.34E+12 n = .00 E = .00 } R097f: S-C3H5 + O -> C2H4 + HCO { A = 6.00E+13 n = .00 E = .00 } R098 : S-C3H5 + OH -> C2H4 + HCO + H { A = 5.00E+12 n = .00 E = .00 } R099 : S-C3H5 + HO2 -> C2H4 + HCO + OH { A = 2.00E+13 n = .00 E = .00 } R100f: S-C3H5 + HCO -> C3H6 + CO { A = 9.00E+13 n = .00 E = .00 } R101f: S-C3H5 + CH3 -> P-C3H4 + CH4 { A = 1.00E+11 n = .00 E = .00 } # Adapted from C2H5/C2H3+O2 R102f: T-C3H5 + O2 -> A-C3H4 + HO2 { A = 1.92E+07 n = 1.02 E = -8.51 } R103f: T-C3H5 + O2 -> P-C3H4 + HO2 { A = 1.34E+06 n = 1.61 E = -1.61 } R104f: S-C3H5 + O2 -> P-C3H4 + HO2 { A = 6.70E+05 n = 1.61 E = -1.61 } R105 : T-C3H5 + O2 -> CH3 + CO + CH2O { A = 4.58E+16 n = -1.39 E = 4.25 } R106f: S-C3H5 + O2 -> CH3CHO + HCO { A = 4.58E+16 n = -1.39 E = 4.25 } # Propanone # --------- # NC7 path from LLNL R107f: C3H5O -> C2H3CHO + H { A = 1.00E+14 n = .00 E = 121.75 } R108f: C3H5O -> C2H3 + CH2O { A = 2.03E+12 n = 0.09 E = 98.58 } R109f: C3H5O + O2 -> C2H3CHO + HO2 { A = 1.00E+12 n = .00 E = 25.10 } # Propene # ------- # A -> 60%-85% C2H6; S -> 20%-50% C2H4; T -> 35% C2H4 # Stoliarov et al. 2002 # Rates fitted at 1.33 bar - 500K to 2400K R110f: C3H6 -> C2H3 + CH3 { A = 4.04E+42 n = -7.67 E = 467.90 } R111f: 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 R112f: A-C3H5 + H -> C3H6 { A = 5.93E+54 n =-11.76 E = 98.53 } # Miller & Klippenstein 2013 # Refitted at P=1bar R113f: C3H6 + H -> C2H4 + CH3 { A = 2.67E+12 n = 0.47 E = 22.72 } R114f: C3H6 + H -> A-C3H5 + H2 { A = 1.42E+04 n = 2.82 E = 14.23 } R115f: C3H6 + H -> S-C3H5 + H2 { A = 8.34E+02 n = 3.25 E = 50.86 } R116f: C3H6 + H -> T-C3H5 + H2 { A = 1.49E+02 n = 3.38 E = 37.28 } # Zador, Jasper, Miller 2009 # Vasu, Hong, Davidson, Hanson 2010 R117f: C3H6 + OH -> A-C3H5 + H2O { A = 9.00E+04 n = 2.59 E = 1.74 } R118f: C3H6 + OH -> S-C3H5 + H2O { A = 3.67E+03 n = 2.89 E = 8.05 } R119f: C3H6 + OH -> T-C3H5 + H2O { A = 4.67E+04 n = 2.47 E = 7.31 } # Adapted from C2H4 - To be revised later R120f: C3H6 + O -> CH2CHO + CH3 { A = 5.09E+07 n = 1.66 E = 2.75 } R121f: C3H6 + O -> C2H5 + HCO { A = 1.95E+08 n = 1.36 E = 3.71 } R122 : C3H6 + O -> C2H3CHO + 2H { A = 3.83E+09 n = 0.88 E = 4.77 } # Rate from C3H8 + X (x0.5) R123f: C3H6 + O -> A-C3H5 + OH { A = 9.95E+04 n = 2.68 E = 15.55 } R124f: C3H6 + HO2 -> A-C3H5 + H2O2 { A = 2.38E+04 n = 2.55 E = 69.00 } R125f: C3H6 + CH3 -> A-C3H5 + CH4 { A = 4.57E-01 n = 3.65 E = 29.93 } # From C2H4 R126f: C3H6 + CH3 -> S-C3H5 + CH4 { A = 1.14E+05 n = 2.00 E = 38.49 } R127f: C3H6 + CH3 -> T-C3H5 + CH4 { A = 5.68E+05 n = 2.00 E = 38.49 } # Hexadiyene # ---------- # Lynch, Annesley, Aul, Yang, Tranter 2013 R128f: A-C3H5 + A-C3H5 -> A-C3H4 + C3H6 { A = 7.50E+11 n = .00 E = .00 } # Matsugi, Suma, Miyoshi 2011 R129 : A-C3H5 + A-C3H5 -> C6H10 { A = 3.18E+13 n = -0.24 E = -2.46 } # From C3H8 (x2) R130 : C6H10 + H -> C6H9 + H2 { A = 1.52E+08 n = 1.86 E = 23.43 } R131 : C6H10 + O -> C6H9 + OH { A = 9.52E+04 n = 2.71 E = 8.81 } R132 : C6H10 + OH -> C6H9 + H2O { A = 3.62E+05 n = 2.44 E = -2.24 } R133 : C6H10 + CH3 -> C6H9 + CH4 { A = 3.02E+00 n = 3.46 E = 29.93 } R134 : C6H10 + HO2 -> C6H9 + H2O2 { A = 1.93E+04 n = 2.60 E = 58.20 } # From C3H6 (x2) R135 : C6H10 + H -> C4H7 + C2H4 { A = 5.34E+12 n = 0.47 E = 22.72 } # Hexadiyenyl radical # ------------------- # From C2H5 R136 : C6H9 + O -> C2H3CHO + A-C3H5 { A = 3.17E+13 n = 0.03 E = -1.65 } R137 : C6H9 + HO2 -> C2H3CHO + A-C3H5 + OH { A = 3.10E+13 n = .00 E = .00 } # From LLNL R138 : C6H9 -> C4H6 + C2H3 { A = 2.50E+13 n = .00 E = 188.28 } #==========================================================================# # # # "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) # # # #==========================================================================# # Diacetylene # ----------- # From C2H H01 : C4H + O2 -> C2H + 2CO { A = 1.00E+13 n = .00 E = -3.16 } # HT backward rate (1900K) as Frank, Just 1980 # Xu, Braun-Unkhoff, Naumann, Frank 2007 H02f: C4H + H -> C4H2 { A = 3.00E+14 n = .00 E = .00 } # Adapted from C2H2 H03f: C4H2 + H -> C4H + H2 { A = 3.20E+09 n = 1.80 E = 125.97 } # Estimated H04f: C2H + C2H -> C4H2 { A = 1.00E+14 n = .00 E = .00 } # Ceursters, Nguyen, Peeters, Nguyen 2000 H05f: C2H2 + C2H -> C4H2 + H { A = 7.80E+13 n = .00 E = .00 } # From P-C3H4 (x2) H06 : C4H2 + O2 -> C2H + CO + HCO { A = 8.00E+14 n = .00 E = 175.43 } # Mitchell, Brunning, Payne, Stief 1988 # Rate about x10 that of C2H2 at 298K # TO BE REVISED H07f: C4H2 + O -> C3H2 + CO { A = 3.70E+09 n = 1.28 E = 10.34 } # Klippenstein & Miller 2005 # Refitted Rate & TROE form H08f: 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 = 0.901 fctA = 12.5 fcB = 0.099 fctB = 10000 fcc = 1.0 fctc = 6674 } H09f: C4H2 + H -> N-C4H3 { A = 1.37E+39 n = -7.87 E = 64.61 } # Senosiain, Klippenstein & Miller 2007 H10f: C4H2 + OH -> C4H + H2O { A = 9.15E+09 n = 1.03 E = 90.99 } H11f: C4H2 + OH -> C4H2O + H { A = 3.41E+10 n = 0.31 E = 5.00 } H12f: C4H2 + OH -> C3H3 + CO { A = 2.11E+23 n = -3.47 E = 31.76 } # Ethynylketene # ------------- # From C4H2+H/OH (HPLx0.5) H13f: C4H2O + H -> C2H2 + HCCO { A = 6.85E+38 n = -7.87 E = 64.61 } H14f: C4H2O + OH -> CH2CO + HCCO { A = 1.53E+11 n = 0.47 E = -1.95 } # C4H3 radicals # ------------- # Wang & Frenklach 1994 ?? H15f: N-C4H3 -> I-C4H3 { A = 4.10E+43 n = -9.50 E = 221.75 } H16f: N-C4H3 + H -> I-C4H3 + H { A = 2.50E+20 n = -1.67 E = 45.19 } H17f: N-C4H3 + H -> C4H4 { A = 2.00E+47 n =-10.26 E = 54.68 } H18f: I-C4H3 + H -> C4H4 { A = 3.40E+43 n = -9.01 E = 50.71 } H19f: N-C4H3 + H -> C2H2 + H2C2 { A = 6.30E+25 n = -3.34 E = 41.88 } H20f: I-C4H3 + H -> C2H2 + H2C2 { A = 2.80E+23 n = -2.55 E = 45.10 } # From C2H3+X H21f: N-C4H3 + H -> C4H2 + H2 { A = 1.50E+13 n = .00 E = .00 } H22f: I-C4H3 + H -> C4H2 + H2 { A = 3.00E+13 n = .00 E = .00 } H23f: N-C4H3 + OH -> C4H2 + H2O { A = 2.50E+12 n = .00 E = .00 } H24f: I-C4H3 + OH -> C4H2 + H2O { A = 5.00E+12 n = .00 E = .00 } H25f: N-C4H3 + O2 -> C4H2 + HO2 { A = 6.70E+05 n = 1.61 E = -1.61 } H26f: I-C4H3 + O2 -> C4H2 + HO2 { A = 1.34E+06 n = 1.61 E = -1.61 } H27f: I-C4H3 + O -> CH2CO + C2H { A = 2.00E+13 n = .00 E = .00 } H28f: I-C4H3 + O2 -> HCCO + CH2CO { A = 1.63E+11 n = .00 E = -7.53 } # From C3H3 + O2 H29f: I-C4H3 + O2 -> HCO + C2H2 + CO { A = 1.70E+05 n = 1.70 E = 6.28 } # Vinylacetylene # -------------- # Decomposition of C4H4 revisited # Problem for diffusion flamelets with C2H2+H2C2 H30f: C2H3 + C2H -> C4H4 { A = 1.00E+14 n = .00 E = .00 } H31f: C2H4 + C2H -> C4H4 + H { A = 1.20E+13 n = .00 E = .00 } # Miller, Klippenstein & Robertson 2000 H32f: C2H3 + C2H2 -> C4H4 + H { A = 1.32E+12 n = 0.16 E = 34.78 } # Adapted from C2H4 - 3kcal H33f: C4H4 + H -> N-C4H3 + H2 { A = 1.27E+05 n = 2.75 E = 48.74 } H34f: C4H4 + H -> I-C4H3 + H2 { A = 6.35E+04 n = 2.75 E = 36.19 } H35f: C4H4 + OH -> N-C4H3 + H2O { A = 2.23E+04 n = 2.75 E = 9.27 } H36f: C4H4 + OH -> I-C4H3 + H2O { A = 1.12E+04 n = 2.75 E = -3.28 } H37f: C4H4 + CH3 -> N-C4H3 + CH4 { A = 1.14E+05 n = 2.00 E = 38.49 } H38f: C4H4 + CH3 -> I-C4H3 + CH4 { A = 5.68E+04 n = 2.00 E = 25.94 } # From C2H2 H39f: C4H4 + O -> C2H3 + HCCO { A = 3.70E+09 n = 1.28 E = 10.34 } # From C2H4 (x1/2) H40f: C4H4 + O -> C3H2 + CH2O { A = 3.58E+04 n = 2.47 E = 3.89 } H41f: C4H4 + O -> C3H3 + HCO { A = 1.95E+08 n = 1.36 E = 3.71 } H42f: C4H4 + OH -> CH2CO + C2H3 { A = 2.10E+01 n = 3.22 E = -1.76 } H43f: C4H4 + OH -> A-C3H5 + CO { A = 1.28E+09 n = 0.73 E = 10.79 } # Hexatriyne & Octotetrayne # ------------------------- # Reactions of C6H2 & C8H2 # Ceursters, Nguyen, Peeters, Nguyen 2000 H44f: C4H2 + C2H -> C6H2 + H { A = 7.80E+13 n = .00 E = .00 } H45f: C2H2 + C4H -> C6H2 + H { A = 7.80E+13 n = .00 E = .00 } H46f: C6H2 + C2H -> C8H2 + H { A = 7.80E+13 n = .00 E = .00 } H47f: C4H2 + C4H -> C8H2 + H { A = 7.80E+13 n = .00 E = .00 } # Estimated H48f: C4H + C4H -> C8H2 { A = 1.00E+14 n = .00 E = .00 } # From C4H2 + OH H49 : C6H2 + OH -> C4H2 + HCCO { A = 3.41E+10 n = 0.31 E = 5.00 } H50 : C8H2 + OH -> C6H2 + HCCO { A = 3.41E+10 n = 0.31 E = 5.00 } #==========================================================================# # # # "Detailed kinetic modelling of butadiene Oxidation at high temperatures" # # A. Laskin, H. Wang, C. Law. # # Int. J. Chem. Kinet. 2000. 32-589 # # # #==========================================================================# # Butadiene # --------- # Baulch et al. 2005 # Full rate to addition B01f: 2 C2H3 -> C4H6 { A = 8.43E+13 n = .00 E = .00 } # Ismail, Georgievskii, Taatjes, et al. 2007 # Rates fitted at P=1.33bar B02f: C2H4 + C2H3 -> C4H6 + H { A = 2.15E+12 n = 0.46 E = 62.65 } B03f: 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 } B04f: C3H6 + C2H3 -> C4H6 + CH3 { A = 7.23E+11 n = .00 E = 20.92 } # Lumping species 12-C4H6 into C4H6 B05f: P-C3H4 + CH3 -> C4H6 + H { A = 8.94E+07 n = 1.14 E = 51.80 } B06f: A-C3H4 + CH3 -> C4H6 + H { A = 2.83E+08 n = 1.06 E = 46.70 } # Wang & Frenklach 1997 B07f: C4H6 -> I-C4H5 + H { A = 5.70E+36 n = -6.27 E = 470.09 } B08f: C4H6 -> N-C4H5 + H { A = 5.30E+44 n = -8.62 E = 517.18 } B09f: C4H6 -> C4H4 + H2 { A = 2.50E+15 n = .00 E = 396.22 } # Adapted from C2H4 - 3kcal # Rate for OH from Vasu, Hanson, et al. 2010 - refitted B10f: C4H6 + H -> N-C4H5 + H2 { A = 1.27E+05 n = 2.75 E = 48.74 } B11f: C4H6 + H -> I-C4H5 + H2 { A = 6.35E+04 n = 2.75 E = 36.19 } B12f: C4H6 + OH -> N-C4H5 + H2O { A = 1.56E+05 n = 2.46 E = 7.78 } B13f: C4H6 + OH -> I-C4H5 + H2O { A = 2.17E+06 n = 2.08 E = 6.58 } B14f: C4H6 + CH3 -> N-C4H5 + CH4 { A = 2.06E-01 n = 3.94 E = 51.98 } B15f: C4H6 + CH3 -> I-C4H5 + CH4 { A = 1.03E-01 n = 3.94 E = 39.43 } B16f: C4H6 + C2H3 -> N-C4H5 + C2H4 { A = 5.00E+13 n = .00 E = 95.54 } B17f: C4H6 + C2H3 -> I-C4H5 + C2H4 { A = 2.50E+13 n = .00 E = 82.84 } # From C2H4 + O B18 : C4H6 + O -> A-C3H5 + CO + H { A = 7.66E+09 n = 0.88 E = 4.77 } B19f: C4H6 + O -> P-C3H4 + CH2O { A = 7.15E+04 n = 2.47 E = 3.89 } B20f: C4H6 + O -> A-C3H5 + HCO { A = 3.89E+08 n = 1.36 E = 3.71 } # Butadienyl radicals # ------------------- # Wang & Frenklach 1994 B21f: C2H3 + C2H2 -> N-C4H5 { A = 9.30E+38 n = -8.76 E = 50.21 } # Wang & Frenklach 1997 B22f: 2 C2H3 -> I-C4H5 + H { A = 1.20E+22 n = -2.44 E = 57.13 } B23f: 2 C2H3 -> N-C4H5 + H { A = 2.40E+20 n = -2.04 E = 64.28 } B24f: 2 C2H3 -> C2H2 + C2H4 { A = 9.60E+11 n = .00 E = .00 } # Wang & Frenklach 1994 B25f: C4H4 + H -> N-C4H5 { A = 1.30E+51 n =-11.92 E = 69.04 } B26f: C4H4 + H -> I-C4H5 { A = 4.90E+51 n =-11.92 E = 74.06 } B27f: N-C4H5 -> I-C4H5 { A = 1.50E+67 n =-16.89 E = 247.30 } # Wang & Frenklach 1997 B28f: N-C4H5 + H -> I-C4H5 + H { A = 3.10E+26 n = -3.35 E = 72.90 } B29f: N-C4H5 + H -> C4H4 + H2 { A = 1.50E+13 n = .00 E = .00 } B30f: N-C4H5 + OH -> C4H4 + H2O { A = 2.50E+12 n = .00 E = .00 } B31f: N-C4H5 + HCO -> C4H6 + CO { A = 5.00E+12 n = .00 E = .00 } B32f: N-C4H5 + H2O2 -> C4H6 + HO2 { A = 1.21E+10 n = .00 E = -2.49 } B33f: N-C4H5 + HO2 -> C4H6 + O2 { A = 6.00E+11 n = .00 E = .00 } # From C2H3 + O B34f: N-C4H5 + O -> A-C3H5 + CO { A = 1.03E+13 n = 0.21 E = -1.79 } # From C2H3 + O2 B35f: N-C4H5 + O2 -> C4H4 + HO2 { A = 6.70E+05 n = 1.61 E = -1.61 } B36 : N-C4H5 + O2 -> A-C3H5 + CO + O { A = 3.03E+11 n = 0.29 E = 0.05 } B37f: N-C4H5 + O2 -> HCO + C2H3CHO { A = 4.58E+16 n = -1.39 E = 4.25 } B38f: I-C4H5 + H -> C4H4 + H2 { A = 3.00E+13 n = .00 E = .00 } B39f: I-C4H5 + H -> C3H3 + CH3 { A = 2.00E+13 n = .00 E = 8.37 } B40f: I-C4H5 + OH -> C4H4 + H2O { A = 5.00E+12 n = .00 E = .00 } B41f: I-C4H5 + HCO -> C4H6 + CO { A = 5.00E+12 n = .00 E = .00 } B42f: I-C4H5 + HO2 -> C4H6 + O2 { A = 6.00E+11 n = .00 E = .00 } B43f: I-C4H5 + H2O2 -> C4H6 + HO2 { A = 1.21E+10 n = .00 E = -2.49 } B44f: I-C4H5 + O2 -> CH2CO + CH2CHO { A = 2.16E+10 n = .00 E = 10.46 } # From C2H5 + O B45f: I-C4H5 + O -> C3H3 + CH2O { A = 3.17E+13 n = 0.03 E = -1.65 } B46f: N-C4H5 + C2H3 -> A1-C6H6 + H2 { A = 1.84E-13 n = 7.07 E = -15.11 } #==========================================================================# # # # "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 -------------------- # # ---------------------- 3 Species ------------------------ # # --------------------- 17 Reactions ---------------------- # # Reactions of N-C6H14 HX01 : N-C6H14 -> N-C5H11 + CH3 { A = 6.03E+18 n = -0.67 E = 362.13 } HX02 : N-C6H14 -> N-C4H9 + C2H5 { A = 1.62E+22 n = -1.49 E = 364.80 } HX03 : N-C6H14 -> N-C3H7 + N-C3H7 { A = 2.62e+22 n = -1.56 E = 367.94 } HX04 : N-C6H14 + H -> C6H13 + H2 { A = 6.16E+07 n = 2.10 E = 22.91 } HX05 : N-C6H14 + O -> C6H13 + OH { A = 1.42E+06 n = 2.56 E = 12.62 } HX06 : N-C6H14 + OH -> C6H13 + H2O { A = 7.49E+06 n = 2.09 E = -2.61 } HX07 : N-C6H14 + O2 -> C6H13 + HO2 { A = 1.70E+13 n = 0.20 E = 209.99 } HX08 : N-C6H14 + HO2 -> C6H13 + H2O2 { A = 6.27E+12 n = 0.21 E = 74.05 } # Reactions of C6H13 (lumped) # Branching ratios 0.2/0.4 HX09 : C6H13 -> N-C4H9 + C2H4 { A = 3.20E+12 n = 0.13 E = 120.84 } HX10 : C6H13 -> N-C3H7 + C3H6 { A = 5.52E+12 n = 0.17 E = 125.16 } HX11 : C6H13 -> C2H5 + C4H8 { A = 2.76E+12 n = 0.17 E = 125.16 } HX12 : C6H13 -> CH3 + C5H10 { A = 2.76E+12 n = 0.17 E = 125.16 } HX13 : C6H13 -> C6H12 + H { A = 1.78E+08 n = 1.63 E = 144.24 } HX14 : C6H13 + HO2 -> C6H13O + OH { A = 7.00E+12 n = .00 E = -4.18 } HX15 : C6H13 + CH3O2 -> C6H13O + CH3O { A = 7.00E+12 n = .00 E = -4.18 } # Reactions of C6H13O HX16 : C6H13O -> N-C5H11 + CH2O { A = 1.19E+18 n = -1.50 E = 84.44 } HX17 : C6H13O -> N-C4H9 + CH3CHO { A = 7.16E+22 n = -2.78 E = 96.22 } HX18 : C6H13O -> N-C3H7 + C2H5 + HCO { A = 4.10E+17 n = -1.31 E = 81.60 } # ------------------- LOW TEMPERATURE -------------------- # # ---------------------- 5 Species ----------------------- # # -------------------- 11 Reactions ---------------------- # /* Commented for now # Formation of ROO HX20 : C6H13 + O2 -> C6H13O2 { A = 1.36E+13 n = -0.08 E = 0.87 } HX21 : C6H13O2 -> C6H13 + O2 { A = 1.71E+23 n = -2.33 E = 158.32 } HX22 : C6H13O2 -> C6H12OOH { A = 1.83E+05 n = 1.70 E = 80.90 } # Reactions of QOOH HX23 : C6H12OOH -> C6H13O2 { A = 7.53E+04 n = 1.25 E = 24.89 } HX24 : C6H12OOH -> C6H12 + HO2 { A = 4.01E+00 n = 3.28 E = 53.36 } HX25 : C6H12OOH -> C6H12O + OH { A = 1.33E+12 n = -0.74 E = 42.56 } HX26 : C6H12OOH + O2 -> C6H13O4 { A = 7.71E+12 n = -0.01 E = -0.06 } # Reactions of O2QOOH HX27 : C6H13O4 -> C6H12OOH + O2 { A = 2.31E+21 n = -1.97 E = 153.05 } HX28 : C6H13O4 -> OC6H11OOH + OH { A = 6.47E+09 n = 0.18 E = 83.01 } # Reactions of OQ'OOH # all products lumped HX29: OC6H11OOH -> C5H10 + CH2CO + OH { A = 3.26E+09 n = 1.93 E = 161.11 } # Reactions of QO # all products lumped HX30: C6H12O + OH -> N-C4H9 + CH2CO + H2O { A = 3.68E+12 n = .00 E = .00 } */ #==========================================================================# # # # "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 -------------------- # # ---------------------- 3 Species ------------------------ # # --------------------- 19 Reactions ---------------------- # # Reactions of N-C7H16 # Rates from LLNL # Multiplied by 3 to match overall decomp rate from exp # (Davidson, Oehlschlaeger, Hanson 2007) HP01 : N-C7H16 -> N-C6H13 + CH3 { A = 8.79E+73 n =-16.61 E = 497.48 } HP02 : N-C7H16 -> N-C5H11 + C2H5 { A = 2.43E+78 n =-17.62 E = 503.75 } HP03 : N-C7H16 -> N-C4H9 + N-C3H7 { A = 4.26E+78 n =-17.71 E = 505.01 } HP04 : N-C7H16 + H -> C7H15 + H2 { A = 9.90E+07 n = 2.06 E = 22.98 } HP05 : N-C7H16 + O -> C7H15 + OH { A = 1.72E+05 n = 2.81 E = 9.46 } HP06 : N-C7H16 + OH -> C7H15 + H2O { A = 9.68E+06 n = 2.08 E = -2.73 } HP07 : N-C7H16 + O2 -> C7H15 + HO2 { A = 2.89E+13 n = 0.20 E = 209.66 } HP08 : N-C7H16 + HO2 -> C7H15 + H2O2 { A = 7.57E+12 n = 0.21 E = 73.78 } # Reactions of C7H15 (lumped) # Branching ratios 0.17/0.33/0.17 # NEW Branching ratios from OH rate about the same at 1000K HP09 : C7H15 -> N-C5H11 + C2H4 { A = 2.72E+12 n = 0.13 E = 120.84 } HP10 : C7H15 -> N-C4H9 + C3H6 { A = 4.55E+12 n = 0.17 E = 125.16 } HP11 : C7H15 -> N-C3H7 + C4H8 { A = 2.28E+12 n = 0.17 E = 125.16 } HP12 : C7H15 -> C2H5 + C5H10 { A = 2.35E+12 n = 0.17 E = 125.16 } HP13 : C7H15 -> CH3 + C6H12 { A = 2.28E+12 n = 0.17 E = 125.16 } HP14 : C7H15 -> C7H14 + H { A = 1.78E+08 n = 1.63 E = 144.24 } 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 (lumped) HP17 : C7H15O -> N-C5H11 + CH3CHO { A = 8.92E+19 n = -2.03 E = 87.88 } HP18 : C7H15O -> N-C4H9 + C2H5 + HCO { A = 2.23E+15 n = -0.70 E = 77.85 } HP19 : C7H15O -> N-C3H7 + N-C3H7 + HCO { A = 6.18E+16 n = -1.36 E = 77.48 } # ------------------- LOW TEMPERATURE -------------------- # # ---------------------- 5 Species ----------------------- # # -------------------- 11 Reactions ---------------------- # /* Commented for now */ # Formation of ROO HP20: C7H15 + O2 -> C7H15O2 { A = 1.68E+13 n = -0.11 E = 1.01 } HP21: C7H15O2 -> C7H15 + O2 { A = 1.92E+22 n = -2.11 E = 156.08 } HP22: C7H15O2 -> C7H14OOH { A = 1.88E+05 n = 1.68 E = 79.51 } # Reactions of QOOH HP23: C7H14OOH -> C7H15O2 { A = 7.64E+05 n = 0.91 E = 25.45 } HP24: C7H14OOH -> C7H14 + HO2 { A = 5.85E+03 n = 2.40 E = 64.08 } HP25: C7H14OOH -> C7H14O + OH { A = 3.97E-10 n = 5.69 E = 1.57 } HP26: C7H14OOH + O2 -> C7H15O4 { A = 1.51E+13 n = -0.09 E = 0.53 } # Reactions of O2QOOH HP27: C7H15O4 -> C7H14OOH + O2 { A = 1.71E+22 n = -2.13 E = 155.32 } HP28: C7H15O4 -> OC7H13OOH + OH { A = 4.25E+10 n = -0.11 E = 81.48 } # Reactions of OQ'OOH # all products lumped HP29: OC7H13OOH -> N-C3H7 + CH3CHO + CH2CO + OH { A = 3.26E+09 n = 1.93 E = 161.11 } # Reactions of QO # all products lumped HP30: C7H14O + OH -> N-C5H11 + CH2CO + H2O { A = 3.68E+12 n = .00 E = .00 } /**/ #==========================================================================# # # # "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 # # # #==========================================================================# # H-abs by H from Cartensen & Dean 2009 # H-abs by OH from Kwok & Atkinson 1995 / Pang, Hanson et al. 2011 # Total decomp rate fitted to McDonald 2012 and Klingbeil et al. 2008 # -> individual rates rescaled with same branching ratios # ------------------- HIGH TEMPERATURE -------------------- # # ---------------------- 3 Species ------------------------ # # --------------------- 73 Reactions ---------------------- # # Reactions of N-C12H26 DD01 : N-C12H26 -> N-C10H21 + C2H5 { A = 1.68E+24 n = -2.11 E = 368.84 } DD02 : N-C12H26 -> N-C9H19 + N-C3H7 { A = 2.46E+24 n = -2.12 E = 371.27 } DD03 : N-C12H26 -> N-C8H17 + N-C4H9 { A = 1.21E+24 n = -2.07 E = 369.64 } DD04 : N-C12H26 -> N-C7H15 + N-C5H11 { A = 1.13E+24 n = -2.06 E = 369.58 } DD05 : N-C12H26 -> N-C6H13 + N-C6H13 { A = 2.59E+24 n = -2.12 E = 369.69 } DD06 : N-C12H26 + H -> C12H25 + H2 { A = 3.59E+08 n = 1.97 E = 23.16 } DD07 : N-C12H26 + O -> C12H25 + OH { A = 3.97E+05 n = 2.76 E = 9.19 } DD08 : N-C12H26 + OH -> C12H25 + H2O { A = 2.18E+07 n = 2.05 E = -2.95 } 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 (lumped) # Branching ratios 0.09/.18 # NEW Branching ratios from OH rate about same at 1000K DD11 : C12H25 -> N-C10H21 + C2H4 { A = 1.44E+12 n = 0.13 E = 120.84 } DD12 : C12H25 -> N-C9H19 + C3H6 { A = 2.48E+12 n = 0.17 E = 125.16 } DD13 : C12H25 -> N-C8H17 + C4H8 { A = 2.48E+12 n = 0.17 E = 125.16 } DD14 : C12H25 -> N-C7H15 + C5H10 { A = 1.24E+12 n = 0.17 E = 125.16 } DD15 : C12H25 -> N-C6H13 + C6H12 { A = 1.24E+12 n = 0.17 E = 125.16 } DD16 : C12H25 -> N-C5H11 + C7H14 { A = 1.24E+13 n = 0.17 E = 125.16 } DD17 : C12H25 -> N-C4H9 + C8H16 { A = 1.24E+13 n = 0.17 E = 125.16 } DD18 : C12H25 -> N-C3H7 + C9H18 { A = 1.24E+12 n = 0.17 E = 125.16 } DD19 : C12H25 -> C2H5 + C10H20 { A = 1.24E+12 n = 0.17 E = 125.16 } DD20 : C12H25 -> C12H24 + H { A = 1.78E+08 n = 1.63 E = 144.24 } DD21 : C12H25 + HO2 -> C12H25O + OH { A = 7.00E+12 n = .00 E = -4.18 } DD22 : C12H25 + CH3O2 -> C12H25O + CH3O { A = 7.00E+12 n = .00 E = -4.18 } # Reactions of C12H25O DD23 : C12H25O -> N-C10H21 + CH3CHO { A = 4.35E+08 n = 1.31 E = 64.79 } DD24 : C12H25O -> N-C9H19 + C2H5 + HCO { A = 8.37E+18 n = -1.84 E = 82.98 } DD25 : C12H25O -> N-C8H17 + N-C3H7 + HCO { A = 9.83E+44 n = -9.70 E = 134.38 } DD26 : C12H25O -> N-C7H15 + N-C4H9 + HCO { A = 8.35E+61 n =-14.50 E = 179.77 } DD27 : C12H25O -> N-C6H13 + N-C5H11 + HCO { A = 4.63E+64 n =-15.38 E = 182.82 } # Reactions of C12H24 (lumped) DD28 : C12H24 -> N-C9H19 + A-C3H5 { A = 9.53E+15 n = -0.18 E = 298.01 } DD32 : C12H24 -> N-C8H17 + C4H7 { A = 1.87E+15 n = 0.04 E = 296.85 } DD31 : C12H24 -> N-C7H15 + C5H9 { A = 1.50E+15 n = -0.02 E = 297.10 } DD30 : C12H24 -> N-C5H11 + C7H13 { A = 2.08E+15 n = -0.04 E = 297.23 } DD29 : C12H24 -> N-C4H9 + C8H15 { A = 1.51E+13 n = 0.52 E = 294.52 } DD33 : C12H24 + H -> C12H23 + H2 { A = 3.70E+13 n = .00 E = 16.32 } DD34 : C12H24 + OH -> C12H23 + H2O { A = 3.00E+13 n = .00 E = 5.15 } # Reactions of C12H23 (lumped) DD35 : C12H23 -> C10H19 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 } DD36 : C12H23 -> C9H17 + C3H6 { A = 1.38E+13 n = 0.17 E = 125.16 } DD37 : C12H23 -> C8H15 + C4H8 { A = 1.38E+13 n = 0.17 E = 125.16 } DD38 : C12H23 -> C7H13 + C5H10 { A = 1.38E+13 n = 0.17 E = 125.16 } DD39 : C12H23 -> C5H9 + C7H14 { A = 1.38E+13 n = 0.17 E = 125.16 } DD40 : C12H23 -> C4H7 + C8H16 { A = 1.38E+13 n = 0.17 E = 125.16 } DD41 : C12H23 -> A-C3H5 + C9H18 { A = 1.38E+13 n = 0.17 E = 125.16 } DD42 : C12H23 -> C2H3 + C10H20 { A = 1.38E+13 n = 0.17 E = 125.16 } # -------------------- LOW TEMPERATURE -------------------- # # ----------------------- 10 Species ---------------------- # # ---------------------- 21 Reactions --------------------- # /* # Reactions of C12H25O2 # Backward rate reduced (x1/6) # to mimic lumping of peroxy species DD50 : C12H25 + O2 -> C12H25O2 { A = 9.52E+12 n = -0.04 E = 0.23 } DD51 : C12H25O2 -> C12H25 + O2 { A = 1.52E+22 n = -2.31 E = 156.59 } DD52 : C12H25O2 -> C12H24OOH { A = 1.13E+06 n = 1.46 E = 80.17 } DD53 : C12H24OOH -> C12H25O2 { A = 4.47E+21 n = -3.86 E = 58.11 } # Reactions of C12H24OOH DD54 : C12H24OOH -> C12H24 + HO2 { A = 2.21E+14 n = -0.81 E = 84.74 } DD55 : C12H24OOH -> C12H24O + OH { A = 3.25E-11 n = 5.92 E = -7.84 } DD56 : C12H24OOH + O2 -> C12H25O4 { A = 1.32E+13 n = -0.08 E = 0.47 } # Reactions of C12H25O4 DD57 : C12H25O4 -> C12H24OOH + O2 { A = 1.92E+23 n = -2.42 E = 157.60 } DD58 : C12H25O4 -> C12H24O3 + OH { A = 1.28E+07 n = 0.89 E = 72.18 } # Reactions of C12H24O3 # lump all decomposition pathways DD59 : C12H24O3 -> N-C8H17 + CH3CHO + CH2CO + OH{ A = 8.95E+14 n = 0.32 E = 171.10 } # Reactions of C12H24O # lump all decomposition pathways DD60 : C12H24O + OH -> N-C8H17 + C2H4 + CH2CO + H2O{ A = 3.09E+13 n = -0.27 E = 1.61 } # Reactions of C8H17O2 DD61 : N-C8H17 + O2 -> C8H17O2 { A = 1.65E+22 n = -2.85 E = 19.78 } DD62 : C8H17O2 -> N-C8H17 + O2 { A = 2.48E+21 n = -1.94 E = 150.73 } DD63 : C8H17O2 -> C8H16OOH { A = 1.11E+06 n = 1.40 E = 79.77 } # Reactions of C8H16OOH DD64 : C8H16OOH -> C8H16O + OH { A = 3.07E+02 n = 2.15 E = 24.57 } DD65 : C8H16OOH -> C8H16 + HO2 { A = 5.11E+06 n = 1.40 E = 70.08 } DD66 : C8H16OOH + O2 -> C8H17O4 { A = 1.16E+11 n = 0.53 E = -3.58 } # Reactions of C8H17O4/C8H16O3 DD67 : C8H17O4 -> C8H16OOH + O2 { A = 1.37E+23 n = -2.37 E = 157.49 } DD68 : C8H17O4 -> C8H16O3 + OH { A = 9.98E+06 n = 1.02 E = 83.92 } DD69 : C8H16O3 -> N-C4H9 + CH3CHO + CH2CO + OH { A = 4.44E+32 n = -4.98 E = 207.98 } DD70 : C8H16O + OH -> N-C6H13 + CH2CO + H2O { A = 3.09E+13 n = -0.27 E = 1.61 } */ #==========================================================================# # # # Additional n-alkyl mechanism # # (based on) # # Lawrence Livermore n-Alkanes Mechanism - ver 2 # # # #==========================================================================# # ------------------- HIGH TEMPERATURE -------------------- # # ---------------------- 21 Species ----------------------- # # --------------------- 70 Reactions ---------------------- # # H-abstractions from Miller & Klippenstein 2013 - HPL # p -> { A = 1.78E+08 n = 1.63 E = 144.24 } # Beta scissions from Ratkiewicz & Truong 2012 - HPL # p -> { A = 1.60E+13 n = 0.13 E = 120.84 } # st -> { A = 1.38E+13 n = 0.17 E = 125.16 } # H-abstraction for alkane from Cartensen & Dean 2009 # p -> { A = 1.40E+07 n = 1.97 E = 34.31 } # s -> { A = 3.80E+07 n = 1.86 E = 23.43 } # Decyl radical # ------------- # Reactions of N-C10H21 NC01 : N-C10H21 -> N-C8H17 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 } NC02 : N-C10H21 -> C10H20 + H { A = 2.04E+10 n = 0.95 E = 141.45 } # Reactions of C10H20 NC03 : C10H20 -> N-C7H15 + A-C3H5 { A = 1.00E+16 n = .00 E = 297.06 } NC04 : C10H20 + H -> C10H19 + H2 { A = 3.70E+13 n = .00 E = 16.32 } NC05 : C10H20 + OH -> C10H19 + H2O { A = 3.00E+13 n = .00 E = 5.15 } # Reactions of C10H19 (lumped) NC06 : C10H19 -> C8H15 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 } NC07 : C10H19 -> C7H13 + C3H6 { A = 1.38E+13 n = 0.17 E = 125.16 } NC08 : C10H19 -> C6H11 + C4H8 { A = 1.38E+13 n = 0.17 E = 125.16 } NC09 : C10H19 -> C5H9 + C5H10 { A = 1.38E+13 n = 0.17 E = 125.16 } NC10 : C10H19 -> C4H7 + C6H12 { A = 1.38E+13 n = 0.17 E = 125.16 } NC11 : C10H19 -> A-C3H5 + C7H14 { A = 1.38E+13 n = 0.17 E = 125.16 } NC12 : C10H19 -> C2H3 + C8H16 { A = 1.38E+13 n = 0.17 E = 125.16 } # Nonyl radical # ------------- # Reactions of N-C9H19 NC13 : N-C9H19 -> N-C7H15 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 } NC14 : N-C9H19 -> C9H18 + H { A = 2.04E+10 n = 0.95 E = 141.45 } # Reactions of C9H18 NC15 : C9H18 -> N-C6H13 + A-C3H5 { A = 1.00E+16 n = .00 E = 297.06 } NC16 : C9H18 + H -> C9H17 + H2 { A = 3.70E+13 n = .00 E = 16.32 } NC17 : C9H18 + OH -> C9H17 + H2O { A = 3.00E+13 n = .00 E = 5.15 } # Reactions of C9H17 (lumped) NC18 : C9H17 -> C7H13 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 } NC19 : C9H17 -> C6H11 + C3H6 { A = 1.38E+13 n = 0.17 E = 125.16 } NC20 : C9H17 -> C5H9 + C4H8 { A = 1.38E+13 n = 0.17 E = 125.16 } NC21 : C9H17 -> C4H7 + C5H10 { A = 1.38E+13 n = 0.17 E = 125.16 } NC22 : C9H17 -> A-C3H5 + C6H12 { A = 1.38E+13 n = 0.17 E = 125.16 } NC23 : C9H17 -> C2H3 + C7H14 { A = 1.38E+13 n = 0.17 E = 125.16 } # Octyl radical # ------------- # Reactions of N-C8H17 NC24 : N-C8H17 -> N-C6H13 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 } NC25 : N-C8H17 -> C8H16 + H { A = 2.04E+10 n = 0.95 E = 141.45 } # Reactions of C8H16 NC26 : C8H16 -> N-C5H11 + A-C3H5 { A = 1.00E+16 n = .00 E = 297.06 } NC27 : C8H16 + H -> C8H15 + H2 { A = 3.70E+13 n = .00 E = 16.32 } NC28 : C8H16 + OH -> C8H15 + H2O { A = 3.00E+13 n = .00 E = 5.15 } # Reactions of C8H15 (lumped) NC29 : C8H15 -> C6H11 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 } NC30 : C8H15 -> C5H9 + C3H6 { A = 1.38E+13 n = 0.17 E = 125.16 } NC31 : C8H15 -> C4H7 + C4H8 { A = 1.38E+13 n = 0.17 E = 125.16 } NC32 : C8H15 -> A-C3H5 + C5H10 { A = 1.38E+13 n = 0.17 E = 125.16 } NC33 : C8H15 -> C2H3 + C6H12 { A = 1.38E+13 n = 0.17 E = 125.16 } # Heptyl radical # -------------- # Reactions of N-C7H15 NC34 : N-C7H15 -> N-C5H11 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 } NC35 : N-C7H15 -> C7H14 + H { A = 2.04E+10 n = 0.95 E = 141.45 } # Reactions of C7H14 NC36 : C7H14 -> N-C4H9 + A-C3H5 { A = 1.00E+16 n = .00 E = 297.06 } NC37 : C7H14 + H -> C7H13 + H2 { A = 3.70E+13 n = .00 E = 16.32 } NC38 : C7H14 + OH -> C7H13 + H2O { A = 3.00E+13 n = .00 E = 5.15 } # Reactions of C7H13 (lumped) NC39 : C7H13 -> C5H9 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 } NC40 : C7H13 -> C4H7 + C3H6 { A = 1.38E+13 n = 0.17 E = 125.16 } NC41 : C7H13 -> A-C3H5 + C4H8 { A = 1.38E+13 n = 0.17 E = 125.16 } NC42 : C7H13 -> C2H3 + C5H10 { A = 1.38E+13 n = 0.17 E = 125.16 } # Hexyl radical # ------------- # Reactions of N-C6H13 NC43 : N-C6H13 -> N-C4H9 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 } NC44 : N-C6H13 -> C6H12 + H { A = 2.04E+10 n = 0.95 E = 141.45 } # Reactions of C6H12 NC45 : C6H12 -> N-C3H7 + A-C3H5 { A = 8.52E+26 n = -3.39 E = 320.10 } NC46 : C6H12 + H -> C6H11 + H2 { A = 3.70E+13 n = .00 E = 16.32 } NC47 : C6H12 + OH -> C6H11 + H2O { A = 3.00E+13 n = .00 E = 5.15 } # Reactions of C6H11 (lumped) NC48 : C6H11 -> C4H7 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 } NC49 : C6H11 -> A-C3H5 + C3H6 { A = 1.38E+13 n = 0.17 E = 125.16 } NC50 : C6H11 -> C2H3 + C4H8 { A = 1.38E+13 n = 0.17 E = 125.16 } # Pentyl radical # -------------- # Reactions of N-C5H11 NC51 : N-C5H11 -> N-C3H7 + C2H4 { A = 3.24E+12 n = 0.32 E = 120.53 } NC52 : N-C5H11 -> C3H6 + C2H5 { A = 1.15E+01 n = 3.03 E = 64.07 } NC53 : N-C5H11 -> C5H10 + H { A = 2.04E+10 n = 0.95 E = 141.45 } # Reactions of C5H10 NC54 : C5H10 -> A-C3H5 + C2H5 { A = 1.00E+16 n = .00 E = 297.06 } NC55 : C5H10 + H -> C5H9 + H2 { A = 3.70E+13 n = .00 E = 16.32 } NC56 : C5H10 + OH -> C5H9 + H2O { A = 3.00E+13 n = .00 E = 5.15 } # Reactions of C5H9 (lumped) NC57 : C5H9 -> A-C3H5 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 } NC58 : C5H9 -> C2H3 + C3H6 { A = 1.38E+13 n = 0.17 E = 125.16 } # Butyl radical # ------------- # Reactions of N-C4H9 NC59 : N-C4H9 -> C2H5 + C2H4 { A = 1.60E+13 n = 0.13 E = 120.84 } NC60 : N-C4H9 -> C4H8 + H { A = 2.04E+10 n = 0.95 E = 141.45 } # Reactions of C4H8 reactions NC61 : C4H8 -> A-C3H5 + CH3 { A = 1.00E+16 n = .00 E = 297.06 } NC62 : C4H8 + H -> C4H7 + H2 { A = 3.70E+13 n = .00 E = 16.32 } NC63 : C4H8 + OH -> C4H7 + H2O { A = 3.00E+13 n = .00 E = 5.15 } # Reactions of C4H7 NC64 : C4H7 -> C2H4 + C2H3 { A = 1.00E+11 n = .00 E = 154.81 } NC65 : C4H7 -> C4H6 + H { A = 1.20E+14 n = .00 E = 206.27 } NC66 : C4H7 + H -> C4H6 + H2 { A = 3.16E+13 n = .00 E = .00 } NC67 : C4H7 + O2 -> C4H6 + HO2 { A = 1.00E+09 n = .00 E = .00 } NC68 : C4H7 + CH3 -> C4H6 + CH4 { A = 8.00E+12 n = .00 E = .00 } NC69 : C4H7 + HO2 -> A-C3H5 + CH2O + OH { A = 7.00E+12 n = .00 E = -4.18 } NC70 : C4H7 + CH3O2 -> A-C3H5 + CH2O + CH3O { A = 7.00E+12 n = .00 E = -4.18 } #==========================================================================# # # # M. Mehl, H. J. Curran, W. J. Pitz, and C. K. Westbrook, 2009 # # LLNL-MI-421507 - Review and release date: December 16, 2009 # # # #==========================================================================# # ------------------- HIGH TEMPERATURE -------------------- # # ---------------------- 15 Species ----------------------- # # --------------------- 73 Reactions ---------------------- # # Reactions of I-C8H18 IC00 : I-C8H18 -> Y-C7H15 + CH3 { A = 6.18E+25 n = -2.46 E = 350.24 } IC01 : I-C8H18 -> T-C4H8 + I-C3H7 + CH3 { A = 2.46E+23 n = -2.01 E = 348.95 } IC02 : I-C8H18 -> 2 T-C4H9 { A = 7.83E+29 n = -3.93 E = 352.08 } IC03 : I-C8H18 + H -> C-C8H17 + H2 { A = 9.08E+00 n = 4.12 E = 7.45 } IC04 : I-C8H18 + O -> C-C8H17 + OH { A = 4.69E+03 n = 3.19 E = 4.52 } IC05 : I-C8H18 + OH -> C-C8H17 + H2O { A = 2.70E+05 n = 2.43 E = -4.04 } 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 } IC09 : I-C8H18 + CH3O2 -> C-C8H17 + CH3O + OH { A = 9.85E+10 n = 0.73 E = 70.89 } # Reactions of C-C8H17 IC10 : C-C8H17 -> Y-C7H14 + CH3 { A = 2.55E+39 n = -7.47 E = 189.48 } IC11 : C-C8H17 -> T-C4H9 + T-C4H8 { A = 4.28E+22 n = -2.81 E = 127.70 } IC12 : C-C8H17 -> T-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 -> T-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-C7H15 -> T-C4H9 + C3H6 { A = 5.14E+23 n = -2.93 E = 131.78 } IC19 : Y-C7H15 -> T-C4H8 + I-C3H7 { A = 5.87E+21 n = -2.57 E = 136.80 } IC20 : Y-C7H15 -> Y-C7H14 + H { A = 6.13E+13 n = 0.03 E = 153.44 } # Reactions of Y-C7H14 IC21 : Y-C7H14 -> T-C4H9 + A-C3H5 { A = 3.98E+26 n = -3.48 E = 320.14 } IC22 : Y-C7H14 -> T-C4H7 + I-C3H7 { A = 5.29E+24 n = -2.55 E = 317.38 } IC23 : Y-C7H14 + H -> X-C7H13 + H2 { A = 2.38E-13 n = 7.67 E = -47.65 } IC24 : Y-C7H14 + OH -> X-C7H13 + H2O { A = 7.76E-09 n = 6.18 E = -41.33 } # Reactions of X-C7H13 IC25 : X-C7H13 -> T-C4H9 + A-C3H4 { A = 8.71E+21 n = -2.43 E = 249.07 } IC26 : X-C7H13 -> T-C4H8 + T-C3H5 { A = 6.32E+18 n = -1.80 E = 182.42 } IC27 : X-C7H13 -> T-C4H7 + C3H6 { A = 2.10E+16 n = -1.09 E = 74.56 } #C28 : X-C7H13 + HO2 -> I-C3H5CHO + I-C3H7 + OH { A = 1.00E+13 n = .00 E = .00 } # Reactions of T-C4H9 # Ratkeiwicz 2011 (x0.5 for lumping) IC29 : T-C4H9 -> C3H6 + CH3 { A = 3.30E+12 n = 0.37 E = 128.58 } IC30 : T-C4H9 -> T-C4H8 + H { A = 5.35E+10 n = 1.06 E = 137.99 } #C31 : T-C4H9 + HO2 -> T-C4H9O + OH { A = 7.00E+12 n = .00 E = -4.18 } #C32 : T-C4H9 + CH3O2 -> T-C4H9O + CH3O { A = 7.00E+12 n = .00 E = -4.18 } # Reactions of T-C4H9O #C33 : T-C4H9O -> I-C3H7 + HCO + H { A = 1.78E+39 n = -7.30 E = 156.05 } #C34 : T-C4H9O -> I-C3H7 + CH2O { A = 7.25E+39 n = -7.59 E = 140.03 } #C35 : T-C4H9O -> CH3COCH3 + CH3 { A = 3.09E+13 n = 0.03 E = 58.87 } # Reactions of T-C4H8 # (not lumped) IC36 : T-C4H8 -> T-C3H5 + CH3 { A = 1.92E+66 n =-14.22 E = 535.97 } IC37 : T-C4H8 + H -> C3H6 + CH3 { A = 5.68E+33 n = -5.72 E = 83.68 } IC38 : T-C4H8 + H -> T-C4H7 + H2 { A = 3.40E+05 n = 2.50 E = 10.43 } IC39 : T-C4H8 + O -> T-C4H7 + OH { A = 1.21E+11 n = 0.70 E = 31.94 } IC40 : T-C4H8 + OH -> T-C4H7 + H2O { A = 5.20E+06 n = 2.00 E = -1.25 } IC41 : T-C4H8 + CH3 -> T-C4H7 + CH4 { A = 4.42E+00 n = 3.50 E = 23.74 } IC42 : T-C4H8 + HO2 -> T-C4H7 + H2O2 { A = 1.93E+04 n = 2.60 E = 58.20 } #C43 : T-C4H8 + O -> I-C3H7 + HCO { A = 1.58E+07 n = 1.76 E = -5.09 } #C44 : T-C4H8 + O -> CH2CO + 2 CH3 { A = 3.33E+07 n = 1.76 E = 0.32 } # Reactions of T-C4H7 # (not lumped) IC45 : T-C4H7 -> A-C3H4 + CH3 { A = 1.23E+47 n = -9.74 E = 310.70 } #C46 : T-C4H7 + O -> I-C3H5CHO + H { A = 6.03E+13 n = .00 E = .00 } #C47 : T-C4H7 + O2 -> I-C3H5CHO + OH { A = 2.47E+13 n = -0.45 E = 96.32 } #C48 : T-C4H7 + O2 -> CH2CO + CH2O + CH3 { A = 7.14E+15 n = -1.21 E = 88.07 } #C49 : T-C4H7 + O2 -> A-C3H4 + CH2O + OH { A = 7.29E+29 n = -5.71 E = 89.75 } #C50 : T-C4H7 + HO2 -> T-C4H7O + OH { A = 7.00E+12 n = .00 E = -4.18 } # Reactions of T-C4H7O # (not lumped) #C51 : T-C4H7O -> I-C3H5CHO + H { A = 5.00E+13 n = .00 E = 121.75 } #C52 : T-C4H7O -> T-C3H5 + CH2O { A = 2.93E+21 n = -2.39 E = 148.91 } #C53 : T-C4H7O + O2 -> I-C3H5CHO + HO2 { A = 3.00E+10 n = .00 E = 6.90 } # Reactions of I-C3H5CHO # (not lumped) #C54 : I-C3H5CHO -> T-C3H5 + HCO { A = 3.05E+23 n = -2.37 E = 415.22 } #C55 : I-C3H5CHO + H -> T-C3H5 + CO + H2 { A = 2.60E+12 n = .00 E = 10.88 } #C56 : I-C3H5CHO + O -> T-C3H5 + CO + OH { A = 7.18E+12 n = .00 E = 5.81 } #C57 : I-C3H5CHO + OH -> T-C3H5 + CO + H2O { A = 2.69E+10 n = 0.76 E = -1.42 } #C58 : I-C3H5CHO + CH3 -> T-C3H5 + CO + CH4 { A = 3.98E+12 n = .00 E = 36.40 } #C59 : I-C3H5CHO + HO2 -> T-C3H5 + CO + H2O2 { A = 1.00E+12 n = .00 E = 49.87 } # Reactions of CH3COCH3 # Revised from LLNL-NC16 # (not lumped) IC60 : CH3COCH3 -> 2 CH3 + CO { A = 1.22E+23 n = -1.99 E = 351.25 } IC61 : CH3COCH3 + H -> CH2CO + CH3 + H2 { A = 2.30E+05 n = 2.72 E = 26.19 } IC62 : CH3COCH3 + O -> CH2CO + CH3 + OH { A = 5.13E+11 n = 0.21 E = 20.46 } IC63 : CH3COCH3 + OH -> CH2CO + CH3 + H2O { A = 3.38E+07 n = 1.74 E = 3.47 } IC64 : CH3COCH3 + O2 -> CH2CO + CH3 + HO2 { A = 6.03E+13 n = .00 E = 202.92 } IC65 : CH3COCH3 + CH3 -> CH2CO + CH3 + CH4 { A = 3.96E+11 n = .00 E = 40.94 } IC66 : CH3COCH3 + HO2 -> CH2CO + CH3 + H2O2 { A = 1.70E+13 n = .00 E = 85.61 } #==========================================================================# # # # Zhong & Bozzelli, Int. J. Chem. Kinet., 1997, 29, 893-913 # # Zhong & Bozzelli, J. Phys. Chem. A, 1998, 102, 3537-3555 # # Robinson & Lindstedt, Comb. Flame, 2011, 158, 666-686 # # # #==========================================================================# # Cyclopentadiene # --------------- # Robinson & Lindstedt 2011 CP01f: C5H6 -> C5H5 + H { A = 3.24E+49 n =-10.01 E = 423.40 } CP02f: C5H6 + H -> C5H5 + H2 { A = 8.59E+07 n = 1.85 E = 13.97 } CP03f: C5H6 + H -> A-C3H5 + C2H2 { A = 7.74E+36 n = -6.81 E = 137.60 } CP04f: C5H6 + O -> C5H5 + OH { A = 4.77E+04 n = 2.71 E = 4.63 } CP05f: C5H6 + OH -> C5H5 + H2O { A = 3.08E+06 n = 2.00 E = .00 } CP06f: C5H6 + O2 -> C5H5 + HO2 { A = 1.00E+14 n = .00 E = 155.44 } CP07f: C5H6 + HO2 -> C5H5 + H2O2 { A = 1.10E+04 n = 2.60 E = 53.97 } CP08f: C5H6 + CH3 -> C5H5 + CH4 { A = 1.80E-01 n = 4.00 E = .00 } # From CH4 + ?? (x0.5) CP09f: C5H6 + C2H3 -> C5H5 + C2H4 { A = 5.55E+04 n = 2.02 E = 13.17 } CP10f: C5H6 + A-C3H5 -> C5H5 + C3H6 { A = 2.15E+01 n = 3.31 E = 106.79 } CP11f: C5H6 + N-C4H5 -> C5H5 + C4H6 { A = 7.30E+10 n = 0.76 E = 63.51 } # Cyclopentadienyl radical # ------------------------ # Moskaleva & Lin 2000 # Knyazev & Slagle 2002 CP16f: C3H3 + C2H2 -> C5H5 { A = 6.87E+55 n =-12.50 E = 175.80 } # Melius, Colvin, Marinov, Pitz, & Senkan 1996 # Sharma & Green 2009 - Rate fitted at P=1bar # PRODUCTS TO BE CHECKED - Should be benzene? CP17 : C5H5 + CH3 -> C5H4CH2 + 2H { A = 4.91E+31 n = -4.85 E = 103.65 } # Murakami et al. 2003 - Total rate # Kislov & Mebel - Branching ratio CP18 : C5H5 + C5H5 -> A2-C10H8 + 2H { A = 6.39E+29 n = -4.03 E = 147.30 } # Robinson & Lindstedt 2011 # estimated CP19f: C5H5 + C5H5 -> C9H7 + CH3 { A = 2.50E+12 n = .00 E = 40.00 } # Kislov & Mebel 2008 - Full entrance rate CP20 : C5H5 + C5H6 -> C9H8 + CH3 { A = 7.86E-01 n = 3.07 E = 23.97 } # Robinson & Lindstedt 2011 CP21f: C5H5 + O -> N-C4H5 + CO { A = 1.27E+14 n = 0.26 E = 16.50 } CP22f: C5H5 + OH -> C4H6 + CO { A = 8.53E+13 n = 0.25 E = 18.20 } CP23f: C5H5 + OH -> C5H5O + H { A = 1.11E+05 n = 1.90 E = 138.60 } CP24f: C5H5 + O2 -> C5H4O + OH { A = 9.11E+15 n = -2.21 E = 10.20 } CP25f: C5H5 + O2 -> C5H5O + O { A = 4.37E+03 n = 2.40 E = 211.50 } CP26f: C5H5 + HO2 -> C5H5O + OH { A = 6.86E+13 n = 0.25 E = 21.30 } # Cyclopentadienoxy radical # ------------------------- # Robinson & Lindstedt 2011 CP27 : C5H5O -> C5H4O + H { A = 8.18E+16 n = -2.32 E = 36.50 } CP28 : C5H5O -> N-C4H5 + CO { A = 2.15E+64 n =-15.14 E = 278.00 } # 1/3 rate from CH3O CP29f: C5H5O + H -> C5H4O + H2 { A = 6.67E+12 n = .00 E = .00 } CP30f: C5H5O + O -> C5H4O + OH { A = 3.33E+12 n = .00 E = .00 } CP31f: C5H5O + OH -> C5H4O + H2O { A = 1.67E+12 n = .00 E = .00 } CP32f: C5H5O + O2 -> C5H4O + HO2 { A = 7.22E+09 n = .00 E = 7.32 } # Cyclopentadienone # ----------------- # Wang & Brezinsky 1998 # Ristori et al. 2001 # (products guessed) CP33 : C5H4O -> 2 C2H2 + CO { A = 6.20E+41 n = -7.87 E = 413.00 } CP34 : C5H4O -> C4H4 + CO { A = 5.00E+11 n = .00 E = 221.80 } # From C2H4+R, C3H6+H # (products guessed) CP35 : C5H4O + H -> C2H3 + C2H2 + CO { A = 2.67E+12 n = 0.47 E = 22.72 } CP36 : C5H4O + O -> C3H3 + HCO + CO { A = 1.02E+08 n = 1.66 E = 2.75 } #==========================================================================# # # # "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 # ------- # Miller & Klippenstein 2003 (1bar) # Updated to include HPL from Harding et al. 2005 BN00f: A1-C6H6 -> A1--C6H5 + H { A = 1.29E+61 n =-12.48 E = 619.59 } # Mebel & Lin 1997 BN01f: A1-C6H6 + H -> A1--C6H5 + H2 { A = 6.02E+08 n = 1.80 E = 68.42 } # Lindsted & Skevis 1994 BN02f: A1-C6H6 + O -> A1--C6H5 + OH { A = 2.00E+13 n = .00 E = 61.50 } # Seta, Nakajima & Miyoshi 2006 BN03f: A1-C6H6 + OH -> A1--C6H5 + H2O { A = 2.34E+04 n = 2.68 E = 3.07 } BN04f: 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 BN05f: A1-C6H6 + O2 -> A1--C6H5 + HO2 { A = 4.34E+14 n = .00 E = 269.00 } # Taatjes, Wang, et al. 2010 # Refitted BN06f: A1-C6H6 + O -> A1O-C6H5O + H { A = 1.99E+07 n = 1.80 E = 16.63 } BN07f: A1-C6H6 + O -> A1OH-C6H6O { A = 1.53E+10 n = 0.92 E = 13.79 } BN08f: A1-C6H6 + O -> C5H6 + CO { A = 1.53E+17 n = -0.89 E = 64.89 } # Phenyl radical # -------------- # Wang et al. 2000 BN09f: 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 } # da Silva, Chen & Bozzelli 2007 # From 3/4-methylphenyl + O2 BN10f: A1--C6H5 + O2 -> A1O-C6H5O + O { A = 8.57E+20 n = -2.27 E = 30.08 } # Frank, Herzler, Just & Wahl 1994 BN11f: A1--C6H5 + O2 -> OC6H4O + H { A = 3.00E+13 n = .00 E = 37.58 } BN12f: A1--C6H5 + O -> A1O-C6H5O { A = 1.00E+14 n = .00 E = .00 } BN13f: A1--C6H5 + OH -> A1O-C6H5O + H { A = 3.00E+13 n = .00 E = .00 } BN14f: A1--C6H5 + HO2 -> A1O-C6H5O + OH { A = 3.00E+13 n = .00 E = .00 } # Tokmakov & Lin 1999/2002 BN15f: 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 BN16f: A1OH-C6H6O -> C5H6 + CO { A = 6.59E+15 n = -0.61 E = 310.11 } BN17f: A1OH-C6H6O -> A1O-C6H5O + H { A = 1.01E+71 n =-15.92 E = 522.12 } # From CH3OH+R BN18f: A1OH-C6H6O + H -> A1O-C6H5O + H2 { A = 4.20E+06 n = 2.10 E = 20.38 } BN19f: A1OH-C6H6O + OH -> A1O-C6H5O + H2O { A = 6.30E+06 n = 2.00 E = 6.28 } BN20f: A1OH-C6H6O + CH3 -> A1O-C6H5O + CH4 { A = 1.00E+07 n = 1.50 E = 41.59 } # Brezinsky et al. 1998 #N21f: 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 BN22f: A1O-C6H5O -> C5H5 + CO { A = 2.90E+10 n = .00 E = 152.40 } # From C2H5 + O (x2) BN23f: A1O-C6H5O + O -> OC6H4O + H { A = 6.34E+13 n = 0.03 E = -1.65 } # From A-C3H5 + O2 - Total rate (x3/2) BN24f: A1O-C6H5O + O2 -> OC6H4O + OH { A = 6.51E+07 n = 1.30 E = 73.92 } # p-Benzoquinone # Thermoprop & Reactions for para # ------------------------------- BN25 : OC6H4O -> C5H4O + CO { A = 7.40E+11 n = .00 E = 246.86 } BN26 : OC6H4O + H -> C5H5O + CO { A = 4.30E+09 n = 1.45 E = 16.18 } BN27 : OC6H4O + O -> CH2CO + C2H2 + 2 CO { A = 3.00E+13 n = .00 E = 20.92 } # Benzyne # ------- # Wang, Laskin, Moriarty, Frenklach 2000 BN28 : O-C6H4 -> C4H2 + C2H2 { A = 1.20E+18 n = -0.34 E = 367.48 } # Wang & Frenklach 1997 BN29f: N-C4H3 + C2H2 -> O-C6H4 + H { A = 6.90E+46 n =-10.01 E = 125.94 } BN30 : O-C6H4 + OH -> C5H5 + CO { A = 1.00E+13 n = .00 E = .00 } #==========================================================================# # # # Toluene chemistry # # # # Oehlschlaeger, Davidson & Hanson, Comb. Flame, 2006, 147, 195-208 # # # #==========================================================================# # Toluene / Benzyl decomposition # ------------------------------ # Tokmakov et al. 2001 (x1.2 to match exp.) # Sheen, Rosado-Reyes, Tsang 2013 (within 2%) 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 } # Assumed products. Other choices: C7H6 + H, c-C7H7 # Rate from Oehlschlaeger et al. 2006 (1.5 atm) T05f: A1CH2-C7H7 -> C5H5 + C2H2 { A = 8.20E+14 n = .00 E = 337.55 } # Toluene # ------- # Oehlschlaeger et al. 2006 (1.5 atm) T06f: A1CH3-C7H8 + H -> A1CH2-C7H7 + H2 { A = 6.47E+00 n = 3.98 E = 14.16 } # From C3H8+O (x0.5) T07f: A1CH3-C7H8 + O -> A1CH2-C7H7 + OH { A = 9.50E+04 n = 2.68 E = 15.55 } # From A1+O (x5/6) T08f: A1CH3-C7H8 + O -> OA1CH3-C7H7O + H { A = 1.66E+07 n = 1.80 E = 16.63 } T09f: A1CH3-C7H8 + O -> HOA1CH3-C7H8O { A = 1.28E+10 n = 0.92 E = 13.79 } # Seta, Nakajima & Miyoshi 2006 # Better match with Vasudevan, Davidson & Hanson 2005 T10f: A1CH3-C7H8 + OH -> A1CH2-C7H7 + H2O { A = 1.77E+05 n = 2.39 E = -2.52 } T11f: A1CH3-C7H8 + OH -> A1OH-C6H6O + CH3 { A = 7.83E+02 n = 2.88 E = 13.48 } T12f: A1CH3-C7H8 + OH -> HOA1CH3-C7H8O + H { A = 3.14E+01 n = 3.37 E = 19.75 } # Oehlschlaeger et al. 2006 (1.5 atm) T13f: A1CH3-C7H8 + O2 -> A1CH2-C7H7 + HO2 { A = 2.18E+07 n = 2.50 E = 192.65 } # Baulch et al. 2005 T14f: A1CH3-C7H8 + HO2 -> A1CH2-C7H7 + H2O2 { A = 9.33E+04 n = 2.50 E = 61.44 } # From C3H8+CH3 (x0.5) T15f: A1CH3-C7H8 + CH3 -> A1CH2-C7H7 + CH4 { A = 4.52E-01 n = 3.65 E = 29.93 } # Heckmann, Hippler & Troe 1996 T16f: A1CH3-C7H8 + A1--C6H5 -> A1CH2-C7H7 + A1-C6H6 { A = 7.94E+13 n = .00 E = 50.00 } # Benzyl radical # -------------- # da Silva & Bozzelli 2012 - P=1atm T17f: A1CH2-C7H7 + O -> A1-C6H6 + HCO { A = 6.98E+12 n = 0.33 E = 2.87 } T18f: A1CH2-C7H7 + O -> A1CHO-C7H6O + H { A = 2.75E+13 n = 0.07 E = 3.06 } # Murakami et al. 2007 - HPL # Canneaux et al. 2008 - Benzylperoxy isomerization # Benzylperoxy in Steady State T19f: A1CH2-C7H7 + O2 -> A1CHO-C7H6O + OH { A = 3.76E+15 n = -1.55 E = 47.37 } # da Silva & Bozzelli 2008 T21f: A1CH2-C7H7 + HO2 -> A1CH2O-C7H7O + OH { A = 1.19E+09 n = 1.03 E = -9.41 } # From A-C3H5 T22 : A1CH2-C7H7 + C3H3 -> A2-C10H8 + 2H { A = 1.88E+38 n = -7.53 E = 99.91 } # Alcoxy Benzyl # ------------- # Choi, Xia, Park & Lin 2000 T23f: A1--C6H5 + CH2O -> A1-C6H6 + HCO { A = 8.55E+04 n = 2.19 E = 0.16 } # Xia & Lin 2000 T24f: A1CH2O-C7H7O -> A1CHO-C7H6O + H { A = 1.27E+13 n = .00 E = 86.19 } # da Silva & Bozzelli 2009 - P=1atm T25f: A1CH2O-C7H7O -> A1--C6H5 + CH2O { A = 7.21E+33 n = -6.21 E = 154.18 } T26f: A1CH2O-C7H7O -> A1-C6H6 + HCO { A = 2.37E+32 n = -6.10 E = 120.54 } # From CH3O (x2/3) T27f: A1CH2O-C7H7O + H -> A1CHO-C7H6O + H2 { A = 1.33E+13 n = .00 E = .00 } T28f: A1CH2O-C7H7O + O -> A1CHO-C7H6O + OH { A = 6.67E+12 n = .00 E = .00 } T29f: A1CH2O-C7H7O + OH -> A1CHO-C7H6O + H2O { A = 3.33E+12 n = .00 E = .00 } T30f: A1CH2O-C7H7O + O2 -> A1CHO-C7H6O + HO2 { A = 4.11E+10 n = .00 E = 7.32 } # Benzaldehyde # ------------ # From CH3CHO - Baulch et al. 2005 # Grela & Colussi 1986 - Loss of H then loss of CO T31 : A1CHO-C7H6O -> A1--C6H5 + CO + H { A = 2.10E+16 n = .00 E = 342.00 } # From CH3CHO T32 : A1CHO-C7H6O + H -> A1--C6H5 + CO + H2 { A = 2.05E+09 n = 1.16 E = 10.06 } T33 : A1CHO-C7H6O + O -> A1--C6H5 + CO + OH { A = 2.92E+12 n = .00 E = 7.57 } T34 : A1CHO-C7H6O + OH -> A1--C6H5 + CO + H2O { A = 2.34E+10 n = .73 E = -4.66 } T35 : A1CHO-C7H6O + CH3 -> A1--C6H5 + CO + CH4 { A = 2.72E+06 n = 1.77 E = 24.77 } # Cresol # All isomers lumped into meta # ---------------------------- # From A1OH/A1O T36f: HOA1CH3-C7H8O -> OA1CH3-C7H7O + H { A = 1.01E+71 n =-15.92 E = 522.12 } T37f: HOA1CH3-C7H8O + H -> OA1CH3-C7H7O + H2 { A = 4.20E+06 n = 2.10 E = 20.38 } T38f: HOA1CH3-C7H8O + O -> OA1CH3-C7H7O + OH { A = 1.30E+05 n = 2.50 E = 20.92 } T39f: HOA1CH3-C7H8O + OH -> OA1CH3-C7H7O + H2O { A = 6.30E+06 n = 2.00 E = 6.28 } T40f: HOA1CH3-C7H8O + CH3-> OA1CH3-C7H7O + CH4 { A = 1.00E+07 n = 1.50 E = 41.59 } T41 : 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 T42f: A1CH3-C7H8 -> A1CH3*-C7H7 + H { A = 8.39E+60 n =-12.48 E = 619.59 } T43f: A1CH3-C7H8 + H -> A1CH3*-C7H7 + H2 { A = 3.91E+08 n = 1.80 E = 68.42 } T44f: A1CH3-C7H8 + O -> A1CH3*-C7H7 + OH { A = 1.60E+13 n = .00 E = 61.50 } T45f: A1CH3-C7H8 + OH -> A1CH3*-C7H7 + H2O { A = 1.36E+04 n = 2.69 E = 2.59 } T46f: A1CH3-C7H8 + CH3 -> A1CH3*-C7H7 + CH4 { A = 1.79E-02 n = 4.46 E = 57.06 } # From A1- T47f: A1CH3*-C7H7 + O -> OA1CH3-C7H7O { A = 1.00E+14 n = .00 E = .00 } T48f: A1CH3*-C7H7 + OH -> OA1CH3-C7H7O + H { A = 3.00E+13 n = .00 E = .00 } T49f: A1CH3*-C7H7 + HO2 -> OA1CH3-C7H7O + OH { A = 3.00E+13 n = .00 E = .00 } # da Silva, Chen & Bozzelli 2007 # Assumed products for methyloxepinoxy decomposition T50f: A1CH3*-C7H7 + O2 -> OA1CH3-C7H7O + O { A = 8.57E+20 n = -2.27 E = 30.08 } T51 : A1CH3*-C7H7 + O2 -> C5H4CH2 + CO2 + H { A = 2.55E+13 n = -0.44 E = -6.90 } T52 : A1CH3*-C7H7 + O2 -> P-C3H4 + C2H3 + 2CO { A = 2.55E+13 n = -0.44 E = -6.90 } #===============================================================================# # # # 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: A1--C6H5 + C2H4 -> A1C2H3-C8H8 + H { 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 = 1.95E+08 n = 1.36 E = 3.71 } ST13f: A1C2H3-C8H8 + O -> A1CHO-C7H6O + T-CH2 { A = 3.58E+04 n = 2.47 E = 3.89 } # Styryl radical # -------------- # Tolkmakov & Lin 2003 ST16f: A1--C6H5 + C2H2 -> A1C2H-C8H6 + H { A = 2.66E+32 n = -5.30 E = 99.52 } ST17f: A1--C6H5 + C2H2 -> A1C2H2-C8H7 { A = 4.80E+44 n = -9.90 E = 73.75 } # Kislov & Mebel 2005 - HPL ST18f: A1C2H2-C8H7 -> A1C2H3*-C8H7 { A = 5.90E+10 n = 0.55 E = 115.34 } # From N-C4H5 ST19f: A1C2H2-C8H7 -> A1C2H-C8H6 + H { A = 1.81E+54 n =-12.69 E = 215.02 } ST20f: A1C2H2-C8H7 + H -> A1C2H-C8H6 + H2 { A = 1.50E+13 n = .00 E = .00 } ST21f: A1C2H2-C8H7 + OH -> A1C2H-C8H6 + H2O { A = 2.50E+12 n = .00 E = .00 } ST22f: A1C2H2-C8H7 + O2 -> A1C2H-C8H6 + HO2 { A = 6.70E+05 n = 1.61 E = -1.61 } # From C2H3 + O ST23f: A1C2H2-C8H7 + O -> A1CH2-C7H7 + CO { A = 1.03E+13 n = 0.21 E = -1.79 } # From C2H3 + O2 ST24 : A1C2H2-C8H7 + O2 -> A1CH2-C7H7 + CO + O { A = 3.03E+11 n = 0.29 E = 0.05 } ST25f: A1C2H2-C8H7 + O2 -> A1CHO-C7H6O + HCO { A = 4.58E+16 n = -1.39 E = 4.25 } # Ethynylbenzene # -------------- # Goulay & Leone 2006 # Woon, Park & Jin-Young 2009 ST26f: A1-C6H6 + C2H -> A1C2H-C8H6 + H { A = 2.00E+14 n = .00 E = .00 } # From A1 (x1/3) ST27f: A1C2H-C8H6 -> A1C2H*-C8H5 + H { A = 4.30E+60 n =-12.48 E = 619.59 } ST28f: A1C2H-C8H6 + H -> A1C2H*-C8H5 + H2 { A = 2.01E+08 n = 1.80 E = 68.42 } ST29f: A1C2H-C8H6 + OH -> A1C2H*-C8H5 + H2O { A = 7.80E+03 n = 2.68 E = 3.07 } # From C2H2 ST30f: A1C2H-C8H6 + O -> A1--C6H5 + HCCO { A = 3.70E+09 n = 1.28 E = 10.34 } ST31f: A1C2H-C8H6 + OH -> A1--C6H5 + CH2CO { A = 2.10E+01 n = 3.22 E = -1.76 } ST32f: A1C2H-C8H6 + OH -> A1CH2-C7H7 + CO { A = 6.40E+08 n = 0.73 E = 10.79 } #==========================================================================# # # # Ethyl-Benzene chemistry # # # # Adapted from C3H8 and Toluene/Benzene chemistry # # # #==========================================================================# # Ethylbenzene # ------------ # Estimated from C3H7+H - HPL EB01f: A1C2H4-C8H9 + H -> A1C2H5-C8H10 { A = 3.61E+13 n = .00 E = .00 } # Estimated from C2H5+CH3 - HPL EB02f: A1CH2-C7H7 + CH3 -> A1C2H5-C8H10 { A = 2.00E+13 n = .00 E = .00 } EB03f: A1--C6H5 + C2H5 -> A1C2H5-C8H10 { A = 2.00E+13 n = .00 E = .00 } # From A1CH3 EB04f: A1C2H5-C8H10 + H -> A1-C6H6 + C2H5 { A = 2.31E+06 n = 2.17 E = 17.42 } EB05f: A1C2H5-C8H10 + OH -> A1OH-C6H6O + C2H5 { A = 7.83E+02 n = 2.88 E = 13.48 } # From C3H8 (x0.5) EB06f: A1C2H5-C8H10 + H -> A1C2H4-C8H9 + H2 { A = 4.68E+07 n = 1.97 E = 34.31 } EB07f: A1C2H5-C8H10 + O -> A1C2H4-C8H9 + OH { A = 9.95E+04 n = 2.68 E = 15.55 } EB08f: A1C2H5-C8H10 + OH -> A1C2H4-C8H9 + H2O { A = 2.67E+03 n = 2.94 E = -1.75 } EB09f: A1C2H5-C8H10 + CH3 -> A1C2H4-C8H9 + CH4 { A = 4.52E-01 n = 3.65 E = 29.93 } EB10f: A1C2H5-C8H10 + HO2 -> A1C2H4-C8H9 + H2O2 { A = 2.38E+04 n = 2.55 E = 69.00 } # N-Ethylbenzene radical # ---------------------- # Tokmakov & Lin 2004 # HPL for both decompositions EB11f: A1C2H4-C8H9 -> A1--C6H5 + C2H4 { A = 1.72E+11 n = 0.78 E = 161.94 } EB12f: A1C2H4-C8H9 -> A1C2H3-C8H8 + H { A = 3.79E+06 n = 1.99 E = 134.33 } # From C3H7 EB13f: A1C2H4-C8H9 + H -> A1C2H3-C8H8 + H2 { A = 1.80E+12 n = .00 E = .00 } EB14f: A1C2H4-C8H9 + OH -> A1C2H3-C8H8 + H2O { A = 2.41E+13 n = .00 E = .00 } EB15f: A1C2H4-C8H9 + O2 -> A1C2H3-C8H8 + HO2 { A = 3.70E+16 n = -1.63 E = 14.30 } EB16f: A1C2H4-C8H9 + CH3 -> A1C2H3-C8H8 + CH4 { A = 3.31E+12 n = .00 E = -3.22 } EB17f: A1C2H4-C8H9 + O -> A1CH2-C7H7 + CH2O { A = 9.60E+13 n = .00 E = .00 } # From NC7 EB18 : A1C2H4-C8H9 + HO2 -> A1CH2-C7H7 + CH2O + OH { A = 7.00E+12 n = .00 E = -4.18 } EB19 : A1C2H4-C8H9 + CH3O2 -> A1CH2-C7H7 + CH2O + CH3O { A = 7.00E+12 n = .00 E = -4.18 } #=========================================================================# # # # Xylene Oxidation Chemistry # # Adapted from Toluene Chemistry # # # #=========================================================================# # Xylene # ------ # From A1CH3 (x2) XY01f: A1CH3CH3-C8H10 -> A1CH3CH2-C8H9 + H { A = 2.12E+13 n = 0.68 E = 373.24 } XY02f: A1CH3CH3-C8H10 -> A1CH3*-C7H7 + CH3 { A = 8.70E+22 n = -1.73 E = 436.01 } # From A1CH3+R (x2) XY03f: A1CH3CH3-C8H10 + H -> A1CH3CH2-C8H9 + H2 { A = 1.29E+01 n = 3.98 E = 14.16 } XY04f: A1CH3CH3-C8H10 + O -> A1CH3CH2-C8H9 + OH { A = 1.90E+05 n = 2.68 E = 15.55 } XY05f: A1CH3CH3-C8H10 + OH -> A1CH3CH2-C8H9 + H2O { A = 3.54E+05 n = 2.39 E = -2.52 } XY06f: A1CH3CH3-C8H10 + O2 -> A1CH3CH2-C8H9 + HO2 { A = 4.36E+07 n = 2.50 E = 192.65 } XY07f: A1CH3CH3-C8H10 + HO2 -> A1CH3CH2-C8H9 + H2O2 { A = 1.87E+05 n = 2.50 E = 61.44 } XY08f: A1CH3CH3-C8H10 + CH3 -> A1CH3CH2-C8H9 + CH4 { A = 9.03E-01 n = 3.65 E = 29.93 } # 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 } # From A1CH2+O XY14f: A1CH3CH2-C8H9 + O -> A1CH3CHO-C8H8O + H { A = 2.75E+13 n = 0.07 E = 3.06 } XY15f: A1CH3CH2-C8H9 + O -> A1CH3-C7H8 + HCO { A = 6.98E+12 n = 0.33 E = 2.87 } # From A1CH2+O2 # Addition from Murakami et al. 2009 # Peroxy isomerization from Canneaux et al. 2008 XY16f: A1CH3CH2-C8H9 + O2 -> A1CH3CHO-C8H8O + OH { A = 1.38E+02 n = 2.42 E = 31.13 } # From A1CH2+HO2 # Assumed unique decomposition into A1CHO+H XY19 : A1CH3CH2-C8H9 + HO2 -> A1CH3CHO-C8H8O + H + OH { A = 1.19E+09 n = 1.03 E = -9.41 } # From A-C3H5 + C3H3 XY20 : A1CH3CH2-C8H9 + C3H3 -> A2CH3-C11H10 + 2H { A = 1.88E+38 n = -7.53 E = 99.91 } # Tolualdehyde # ------------ # From A1CH3 & A1CHO decomposition XY21f: A1CH3CHO-C8H8O -> A1CHOCH2-C8H7O + H { A = 1.56E+13 n = 0.68 E = 373.24 } XY22 : A1CH3CHO-C8H8O -> A1--C6H5 + CO + CH3 { A = 4.35E+22 n = -1.73 E = 436.01 } XY23 : A1CH3CHO-C8H8O -> A1CH3*-C7H7 + CO + H { A = 2.10E+16 n = .00 E = 342.00 } # From A1CH3+R XY24f: A1CH3CHO-C8H8O + H -> A1CHOCH2-C8H7O + H2 { A = 6.47E+00 n = 3.98 E = 14.16 } XY25f: A1CH3CHO-C8H8O + O -> A1CHOCH2-C8H7O + OH { A = 9.50E+04 n = 2.68 E = 15.55 } XY26f: A1CH3CHO-C8H8O + OH -> A1CHOCH2-C8H7O + H2O { A = 1.77E+05 n = 2.39 E = -2.52 } XY27f: A1CH3CHO-C8H8O + CH3 -> A1CHOCH2-C8H7O + CH4 { A = 4.52E-01 n = 3.65 E = 29.93 } # From A1CHO+R XY28 : A1CH3CHO-C8H8O + H -> A1CH3*-C7H7 + CO + H2 { A = 2.05E+09 n = 1.16 E = 10.06 } XY29 : A1CH3CHO-C8H8O + O -> A1CH3*-C7H7 + CO + OH { A = 2.92E+12 n = .00 E = 7.57 } XY30 : A1CH3CHO-C8H8O + OH -> A1CH3*-C7H7 + CO + H2O { A = 2.34E+10 n = 0.73 E = -4.66 } XY31 : A1CH3CHO-C8H8O + CH3 -> A1CH3*-C7H7 + CO + CH4 { A = 2.72E+06 n = 1.77 E = 24.77 } # Tolualdehyde radical # -------------------- # From A1CH2+O XY32f: A1CHOCH2-C8H7O + O -> A1CHOCHO-C8H6O2 + H { A = 2.75E+13 n = 0.07 E = 3.06 } XY33f: A1CHOCH2-C8H7O + O -> A1CHO-C7H6O + HCO { A = 6.98E+12 n = 0.33 E = 2.87 } # From A1CH2+HO2 # Assumed unique decomposition into A1CHO+H XY33 : A1CHOCH2-C8H7O + HO2 -> A1CHOCHO-C8H6O2 + H + OH { A = 1.19E+09 n = 1.03 E = -9.41 } # Phthalaldehyde # -------------- # From A1CHO decomposition (x2) XY34 : A1CHOCHO-C8H6O2 -> A1--C6H5 + 2 CO + H { A = 4.20E+16 n = .00 E = 342.00 } # From A1CHO+R (x2) XY35 : A1CHOCHO-C8H6O2 + H -> A1CHO-C7H6O + CO + H { A = 4.10E+09 n = 1.16 E = 10.06 } XY36 : A1CHOCHO-C8H6O2 + O -> A1CHO-C7H6O + CO + O { A = 5.84E+12 n = .00 E = 7.57 } XY37 : A1CHOCHO-C8H6O2 + OH -> A1CHO-C7H6O + CO + OH { A = 4.68E+10 n = 0.73 E = -4.66 } XY38 : A1CHOCHO-C8H6O2 + CH3 -> A1CHO-C7H6O + CO + CH3 { A = 5.44E+06 n = 1.77 E = 24.77 } #==========================================================================# # # # Indene chemistry # # Adapted from Cyclopentadiene # # # #==========================================================================# # Indene # ------ # Kislov & Mebel 2007 # Rate estimated I00f: A1--C6H5 + C3H3 -> C9H8 { A = 1.00E+13 n = .00 E = .00 } # Kislov & Mebel 2007 I01f: A1CH2-C7H7 + C2H2 -> C9H8 + H { A = 3.16E+04 n = 2.48 E = 46.28 } I02f: C9H8 -> C9H7 + H { A = 3.24E+49 n =-10.01 E = 423.40 } I03f: C9H8 + H -> C9H7 + H2 { A = 8.59E+07 n = 1.85 E = 13.97 } 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 #I10 : C9H8 + O -> O-C6H4 + C2H3 + CO + H { A = 1.02E+08 n = 1.66 E = 2.75 } # Indenyl radical # 2/5 of the rate for C5H5 # ------------------------ I12 : C9H7 + C5H5 -> A3-C14H10 + 2H { A = 2.56E+29 n = -4.03 E = 147.30 } I13 : C9H7 + CH3 -> A2-C10H8 + 2H { A = 1.96E+31 n = -4.85 E = 103.65 } # TEST - GB #I14 : C9H7 -> C5H5 + C4H2 { A = 1.00E+10 n= .00 E = 250.00 } I15 : C9H7 + O -> A1C2H2-C8H7 + CO { A = 5.08E+13 n = 0.26 E = 16.50 } I16 : C9H7 + OH -> A1C2H3-C8H8 + CO { A = 3.41E+13 n = 0.25 E = 18.20 } I17 : C9H7 + OH -> C9H6O + 2H { A = 4.44E+04 n = 1.90 E = 138.60 } I18 : C9H7 + O2 -> C9H6O + OH { A = 3.64E+15 n = -2.21 E = 10.20 } I19 : C9H7 + O2 -> C9H6O + O + H { A = 1.75E+03 n = 2.40 E = 211.50 } I20 : C9H7 + HO2 -> C9H6O + OH + H { A = 2.74E+13 n = 0.25 E = 21.30 } # From A-C3H5 + C3H3 I21 : C9H7 + C3H3 -> A2R5-C12H8 + 2H { A = 1.88E+38 n = -7.53 E = 99.91 } # Indenone # -------- I22 : C9H6O -> O-C6H4 + C2H2 + CO { A = 6.20E+41 n = -7.87 E = 413.00 } I23 : C9H6O + H -> A1C2H2-C8H7 + CO { A = 1.37E+09 n = 1.46 E = 5.67 } I24 : C9H6O + O -> O-C6H4 + CH2CO + CO { A = 1.02E+08 n = 1.66 E = 2.75 } #==========================================================================# # # # Napthalene Oxidation Chemistry # # Adapted from Benzene # # # #==========================================================================# # Naphthalene # 5/3 of the rate for A1 # ---------------------- NP01f: A2-C10H8 -> A2--C10H7 + H { A = 8.60E+60 n =-12.48 E = 619.55 } NP02f: A2-C10H8 + H -> A2--C10H7 + H2 { A = 4.01E+08 n = 1.80 E = 68.42 } NP03f: A2-C10H8 + OH -> A2--C10H7 + H2O { A = 3.90E+04 n = 2.68 E = 3.07 } NP04f: A2-C10H8 -> A2*-C10H7 + H { A = 8.60E+60 n =-12.48 E = 619.55 } NP05f: A2-C10H8 + H -> A2*-C10H7 + H2 { A = 4.01E+08 n = 1.80 E = 68.42 } NP06f: A2-C10H8 + OH -> A2*-C10H7 + H2O { A = 3.90E+04 n = 2.68 E = 3.07 } NP07f: A2-C10H8 + O -> A2O-C10H7O + H { A = 3.32E+07 n = 1.80 E = 16.63 } NP08f: A2-C10H8 + O -> A2OH-C10H8O { A = 2.55E+10 n = 0.92 E = 13.79 } NP09f: A2-C10H8 + O -> C9H8 + CO { A = 2.55E+17 n = -0.89 E = 64.89 } NP10f: A2-C10H8 + OH -> A2OH-C10H8O + H { A = 2.20E+02 n = 3.25 E = 23.39 } # Naphthyl radical # Full rate for A1- # ----------------- # Park, Nguyen, Xu, Lin 2009 NP11f: A2--C10H7 -> A2*-C10H7 { A = 1.51E+07 n = .00 E = 184.85 } NP12f: A2--C10H7 + O2 -> A2O-C10H7O + O { A = 8.57E+20 n = -2.27 E = 30.08 } NP13f: A2*-C10H7 + O2 -> A2O-C10H7O + O { A = 8.57E+20 n = -2.27 E = 30.08 } NP14 : A2--C10H7 + O2 -> C9H6O + CO + H { A = 3.00E+13 n = .00 E = 37.58 } NP15 : A2*-C10H7 + O2 -> C9H6O + CO + H { A = 3.00E+13 n = .00 E = 37.58 } NP16f: A2--C10H7 + O -> A2O-C10H7O { A = 1.00E+14 n = .00 E = .00 } NP17f: A2*-C10H7 + O -> A2O-C10H7O { A = 1.00E+14 n = .00 E = .00 } NP18f: A2--C10H7 + OH -> A2O-C10H7O + H { A = 3.00E+13 n = .00 E = .00 } NP19f: A2*-C10H7 + OH -> A2O-C10H7O + H { A = 3.00E+13 n = .00 E = .00 } # Naphthol # Full rate for A1OH # ------------------ NP20f: A2OH-C10H8O -> C9H8 + CO { A = 8.62E+15 n = -0.61 E = 310.11 } NP21f: A2OH-C10H8O -> A2O-C10H7O + H { A = 1.01E+71 n =-15.92 E = 522.12 } NP22f: A2OH-C10H8O + H -> A2O-C10H7O + H2 { A = 6.83E+01 n = 3.40 E = 30.26 } NP23f: A2OH-C10H8O + OH -> A2O-C10H7O + H2O { A = 1.73E+01 n = 3.40 E = -4.78 } NP24f: A2OH-C10H8O + CH3 -> A2O-C10H7O + CH4 { A = 3.70E-04 n = 4.70 E = 20.20 } # Naphthoxy radical # Full rate for A1O # ----------------- NP25f: A2O-C10H7O -> C9H7 + CO { A = 2.90E+10 n = .00 E = 152.40 } NP26 : A2O-C10H7O + O -> C9H6O + CO + H { A = 1.68E+14 n = .00 E = .00 } NP27 : A2O-C10H7O + O2 -> C9H6O + CO + OH { A = 6.51E+07 n = 1.30 E = 73.92 } #=========================================================================# # # # alpha-MethylNaphthalene chemistry # # Adapted from Toluene chemistry # # # #=========================================================================# # MethylNaphthalene # ----------------- MN01f: A2CH3-C11H10 + H -> A2-C10H8 + CH3 { A = 2.31E+06 n = 2.17 E = 17.42 } MN02f: A2CH3-C11H10 + OH -> A2OH-C10H8O + CH3 { A = 7.83E+02 n = 2.88 E = 13.48 } # Collision Limit at 298K MN03f: A2CH3-C11H10 -> A2CH2-C11H9 + H { A = 1.25E+18 n = -0.60 E = 396.59 } MN04f: A2CH3-C11H10 -> A2--C10H7 + CH3 { A = 3.20E+34 n = -5.02 E = 478.03 } MN05f: A2CH2-C11H9 + H -> A2--C10H7 + CH3 { A = 5.83E+67 n =-14.15 E = 285.89 } MN06f: A2CH2-C11H9 -> C9H7 + C2H2 { A = 8.20E+14 n = .00 E = 337.55 } MN07f: A2CH3-C11H10 + H -> A2CH2-C11H9 + H2 { A = 6.47E+00 n = 3.98 E = 14.16 } MN08f: A2CH3-C11H10 + O -> A2CH2-C11H9 + OH { A = 1.18E+00 n = 4.09 E = 10.65 } MN09f: A2CH3-C11H10 + OH -> A2CH2-C11H9 + H2O { A = 1.77E+05 n = 2.39 E = -2.52 } MN10f: A2CH3-C11H10 + O2 -> A2CH2-C11H9 + HO2 { A = 2.18E+07 n = 2.50 E = 192.65 } MN11f: A2CH3-C11H10 + CH3 -> A2CH2-C11H9 + CH4 { A = 1.73E+01 n = 3.44 E = 43.47 } MN12f: A2CH3-C11H10 + HO2 -> A2CH2-C11H9 + H2O2 { A = 9.33E+04 n = 2.50 E = 61.44 } MN13 : A2CH3-C11H10 + O -> A2-C10H8 + CO + 2 H { A = 1.10E+13 n = .00 E = 18.96 } MN14 : A2CH3-C11H10 + O -> C9H7 + CH3 + CO { A = 1.47E+13 n = .00 E = 18.96 } # Methylene-Naphthyl # ------------------ MN15f: A2CH2-C11H9 + O -> A2-C10H8 + HCO { A = 6.98E+12 n = 0.33 E = 2.87 } MN16f: A2CH2-C11H9 + O -> A2CHO-C11H8O + H { A = 2.75E+13 n = 0.07 E = 3.06 } MN17f: A2CH2-C11H9 + O2 -> A2CHO-C11H8O + OH { A = 3.76E+15 n = -1.55 E = 47.37 } MN18f: A2CH2-C11H9 + HO2 -> A2CH2O-C11H9O + OH { A = 1.19E+09 n = 1.03 E = -9.41 } MN19 : A2CH2-C11H9 + C3H3 -> A3-C14H10 + 2H { A = 1.88E+38 n = -7.53 E = 99.91 } # Methoxy-Naphthyl # ---------------- MN20f: A2CH2O-C11H9O -> A2CHO-C11H8O + H { A = 1.27E+13 n = .00 E = 86.19 } MN21f: A2CH2O-C11H9O -> A2--C10H7 + CH2O { A = 7.21E+33 n = -6.21 E = 154.18 } MN22f: A2CH2O-C11H9O + H -> A2CHO-C11H8O + H2 { A = 1.33E+13 n = .00 E = .00 } MN23f: A2CH2O-C11H9O + O -> A2CHO-C11H8O + OH { A = 6.67E+12 n = .00 E = .00 } MN24f: A2CH2O-C11H9O + OH -> A2CHO-C11H8O + H2O { A = 3.33E+12 n = .00 E = .00 } MN25f: A2CH2O-C11H9O + O2 -> A2CHO-C11H8O + HO2 { A = 4.11E+10 n = .00 E = 7.32 } # Naphthaldehyde # -------------- MN26 : A2CHO-C11H8O -> A2--C10H7 + CO + H { A = 2.10E+16 n = .00 E = 342.00 } MN27 : A2CHO-C11H8O + H -> A2--C10H7 + CO +H2 { A = 2.05E+09 n = 1.16 E = 10.06 } MN28 : A2CHO-C11H8O + O -> A2--C10H7 + CO +OH { A = 2.92E+12 n = .00 E = 7.57 } MN29 : A2CHO-C11H8O + OH -> A2--C10H7 + CO +H2O { A = 2.34E+10 n = 0.73 E = -4.66 } MN30 : A2CHO-C11H8O + CH3-> A2--C10H7 + CO +CH4 { A = 2.72E+06 n = 1.77 E = 24.77 } #==========================================================================# # # # PAH chemistry # # HACA Based Mechanism # # # #==========================================================================# # Fulvene # ------- # Jasper & Hansen 2013 - 1atm P01f: C5H4CH2 + H -> A1-C6H6 + H { A = 1.14E+32 n = -4.88 E = 79.05 } # Senosiain & Miller 2007 (JPCA) P02f: N-C4H5 + C2H2 -> C5H4CH2 + H { A = 4.62E+15 n = -0.89 E = 38.25 } P03f: I-C4H5 + C2H2 -> C5H4CH2 + H { A = 6.80E+24 n = -3.45 E = 85.09 } # Miller & Klippenstein 2003 P04f: C5H4CH2 -> A1-C6H6 { A = 1.45E+45 n = -8.90 E = 405.86 } P05f: C5H4CH2 -> A1--C6H5 + H { A = 2.24E+68 n =-14.65 E = 596.54 } # Benzene # ------- # Wang & Frenklach 1997 P06f: N-C4H3 + C2H2 -> A1--C6H5 { A = 9.60E+70 n =-17.77 E = 130.96 } # Senosiain & Miller 2007 (JPCA) P07f: N-C4H5 + C2H2 -> A1-C6H6 + H { A = 1.38E+16 n = -1.00 E = 37.24 } P08f: I-C4H5 + C2H2 -> A1-C6H6 + H { A = 1.67E+23 n = -3.30 E = 104.43 } # Miller, Klippenstein, Georgievskii, Harding, Allen, Simmonett 2010 P09 : 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 P10f: C3H3 + C3H3 -> C5H4CH2 { A = 8.25E+46 n =-10.10 E = 70.96 } P11f: C3H3 + C3H3 -> A1-C6H6 { A = 1.07E+45 n = -9.57 E = 71.19 } P12f: C3H3 + C3H3 -> A1--C6H5 + H { A = 5.77E+37 n = -7.00 E = 131.82 } # Tokmakov & Lin 2004 P13f: A1--C6H5 + C2H4 -> A1-C6H6 + C2H3 { A = 9.45E-03 n = 4.47 E = 18.71 } # Naphthalene # ----------- # From A1 (x1/3) P14f: A1C2H-C8H6 + C2H -> A2--C10H7 { A = 6.67E+13 n = .00 E = .00 } P15f: A1C2H3-C8H8 + C2H -> A2-C10H8 + H { A = 6.67E+13 n = .00 E = .00 } # Kislov & Mebel 2005 P16f: A1C2H*-C8H5 + C2H2 -> A2--C10H7 { A = 1.34E+04 n = 2.50 E = 5.37 } P17f: A1C2H2-C8H7 + C2H2 -> A2-C10H8 + H { A = 2.62E+06 n = 2.00 E = 19.16 } P18f: A1C2H3*-C8H7 + C2H2 -> A2-C10H8 + H { A = 3.02E+03 n = 2.55 E = 13.31 } # From A1 (x1/3) P19f: A1C2H-C8H6 + C2H3 -> A2-C10H8 + H { A = 4.50E+16 n = -1.15 E = 61.01 } # From A1- P20f: A1C2H*-C8H5 + C2H4 -> A2-C10H8 + H { A = 3.62E+28 n = -4.24 E = 99.85 } # Aguilera-Iparraguirre & Klopper 2007 # Total entrance channel rate P21f: A1--C6H5 + C4H4 -> A2-C10H8 + H { A = 1.26E+04 n = 2.61 E = 6.00 } # From A1 (x2/3) P22f: A2-C10H8 + C2H -> A2C2HA-C12H8 + H { A = 1.67E+14 n = .00 E = .00 } P23f: A2-C10H8 + C2H -> A2C2HB-C12H8 + H { A = 1.67E+14 n = .00 E = .00 } # Park, Nguyen, Xu, Lin 2009 P24f: A2--C10H7 + C2H2 -> A2R5-C12H8 + H { A = 2.81E+07 n = 1.77 E = 9.37 } P25f: A2*-C10H7 + C2H2 -> A2C2HB-C12H8 + H { A = 5.38E+07 n = 1.65 E = 10.71 } # From A1 (x2/3) P26f: A2-C10H8 + C2H3 -> A2C2H2A-C12H9 + H2 { A = 9.01E+16 n = -1.15 E = 61.01 } P27f: A2-C10H8 + C2H3 -> A2C2H2B-C12H9 + H2 { A = 9.01E+16 n = -1.15 E = 61.01 } # From A1- P28f: A2--C10H7 + C2H4 -> A2C2H2A-C12H9 + H2 { A = 3.62E+28 n = -4.24 E = 99.85 } P29f: A2*-C10H7 + C2H4 -> A2C2H2B-C12H9 + H2 { A = 3.62E+28 n = -4.24 E = 99.85 } # From A1C2H2 P30f: A2C2H2A-C12H9 -> A2C2HA-C12H8 + H { A = 1.81E+54 n =-12.69 E = 215.02 } P31f: A2C2H2A-C12H9 + H -> A2C2HA-C12H8 + H2 { A = 1.50E+13 n = .00 E = .00 } P32f: A2C2H2A-C12H9 + OH -> A2C2HA-C12H8 + H2O { A = 2.50E+12 n = .00 E = .00 } P33f: A2C2H2B-C12H9 -> A2C2HB-C12H8 + H { A = 1.81E+54 n =-12.69 E = 215.02 } P34f: A2C2H2B-C12H9 + H -> A2C2HB-C12H8 + H2 { A = 1.50E+13 n = .00 E = .00 } P35f: A2C2H2B-C12H9 + OH -> A2C2HB-C12H8 + H2O { A = 2.50E+12 n = .00 E = .00 } # From A1 (x1/6) P36f: A2C2HA-C12H8 -> A2C2HA*-C12H7 + H { A = 2.15E+60 n =-12.48 E = 619.55 } P37f: A2C2HA-C12H8 + H -> A2C2HA*-C12H7 + H2 { A = 1.00E+08 n = 1.80 E = 68.42 } P38f: A2C2HA-C12H8 + OH -> A2C2HA*-C12H7 + H2O { A = 3.90E+03 n = 2.68 E = 3.07 } P39f: A2C2HB-C12H8 -> A2C2HB*-C12H7 + H { A = 2.15E+60 n =-12.48 E = 619.55 } P40f: A2C2HB-C12H8 + H -> A2C2HB*-C12H7 + H2 { A = 1.00E+08 n = 1.80 E = 68.42 } P41f: A2C2HB-C12H8 + OH -> A2C2HB*-C12H7 + H2O { A = 3.90E+03 n = 2.68 E = 3.07 } # Acenaphthalene # -------------- # Kislov & Mebel 2005 P42f: A2C2H2A-C12H9 -> A2R5-C12H8 + H { A = 2.88E+11 n = 0.23 E = 71.24 } # Lifshitz, Tambura & Dubnikova 2007 P43f: A2C2HA-C12H8 + H -> A2R5-C12H8 + H { A = 3.52E+12 n = .00 E = 55.90 } # From A1 (x2/3) P44f: A2R5-C12H8 -> A2R5--C12H7 + H { A = 8.60E+60 n =-12.48 E = 619.55 } P45f: A2R5-C12H8 + H -> A2R5--C12H7 + H2 { A = 4.01E+08 n = 1.80 E = 68.42 } P46f: A2R5-C12H8 + OH -> A2R5--C12H7 + H2O { A = 1.34E+04 n = 2.68 E = 3.07 } # From A1 (x2/3) P47f: A2R5-C12H8 + C2H -> A2R5C2H-C14H8 + H { A = 1.67E+14 n = .00 E = .00 } # From A2* P48f: A2R5--C12H7 + C2H2 -> A2R5C2H-C14H8 + H { A = 5.38E+07 n = 1.65 E = 10.71 } # From A1 (x2/3) P49f: A2R5-C12H8 + C2H3 -> A2R5C2H2-C14H9 + H2 { A = 9.01E+16 n = -1.15 E = 61.01 } # From A1- P50f: A2R5--C12H7 + C2H4 -> A2R5C2H2-C14H9 + H2 { A = 3.62E+28 n = -4.24 E = 99.85 } # From A1C2H2 P51f: A2R5C2H2-C14H9 -> A2R5C2H-C14H8 + H { A = 2.09E+38 n = -7.74 E = 196.19 } P52f: A2R5C2H2-C14H9 + H -> A2R5C2H-C14H8 + H2 { A = 1.65E+11 n = 0.49 E = 44.48 } P53f: A2R5C2H2-C14H9 + OH-> A2R5C2H-C14H8 + H2O { A = 2.50E+12 n = .00 E = .00 } # From A1 (x1/6) P54f: A2R5C2H-C14H8 -> A2R5C2H*-C14H7 + H { A = 2.15E+60 n =-12.48 E = 619.55 } P55f: A2R5C2H-C14H8 + H -> A2R5C2H*-C14H7 + H2 { A = 1.00E+08 n = 1.80 E = 68.42 } P56f: A2R5C2H-C14H8 + OH-> A2R5C2H*-C14H7 + H2O { A = 3.90E+03 n = 2.68 E = 3.07 } # Biphenyl # -------- # Park, Burova,, Rodgers & Lin 1999 # Fitted exp rate P57f: A1-C6H6 + A1--C6H5 -> P2-C12H10 + H { A = 9.55E+11 n = .00 E = 9.07 } # Tranter, Klippenstein, Harding, Giri, Yang, Keifer 2010 P58f: A1--C6H5 + A1--C6H5 -> P2-C12H10 { A = 7.34E+20 n = -2.34 E = 17.26 } P59f: A1--C6H5 + A1--C6H5 -> P2--C12H9 + H { A = 2.44E+13 n = 0.89 E = 180.66 } # From A1 (x2/3) P60f: P2-C12H10 -> P2--C12H9 + H { A = 8.60E+60 n =-12.48 E = 619.55 } P61f: P2-C12H10 + H -> P2--C12H9 + H2 { A = 4.01E+08 n = 1.80 E = 68.42 } P62f: P2-C12H10 + OH -> P2--C12H9 + H2O { A = 1.34E+04 n = 2.68 E = 3.07 } # Phenanthrene # ------------ # From A1C2H3* P63f: P2--C12H9 + C2H2 -> A3-C14H10 + H { A = 3.02E+03 n = 2.55 E = 13.31 } # From P2 (x1/3) P64f: A1C2H-C8H6 + A1--C6H5 -> A3-C14H10 + H { A = 3.18E+11 n = .00 E = 9.07 } # From P2 & P2- P65f: A1C2H*-C8H5 + A1-C6H6 -> A3-C14H10 + H { A = 9.55E+11 n = .00 E = 9.07 } P66f: A1C2H*-C8H5 + A1--C6H5 -> A3-C14H10 { A = 1.39E+13 n = .00 E = 0.47 } # From A1 (x1/6) P67f: A2C2HA-C12H8 + C2H -> A3--C14H9 { A = 3.33E+13 n = .00 E = .00 } P68f: A2C2HB-C12H8 + C2H -> A3--C14H9 { A = 3.33E+13 n = .00 E = .00 } # From A1C2H* P69f: A2C2HA*-C12H7 + C2H2 -> A3*-C14H9 { A = 1.34E+04 n = 2.50 E = 5.37 } P70f: A2C2HB*-C12H7 + C2H2 -> A3*-C14H9 { A = 1.34E+04 n = 2.50 E = 5.37 } # From A1C2H2 P71f: A2C2H2A-C12H9 + C2H2 -> A3-C14H10 + H { A = 2.62E+06 n = 2.00 E = 19.16 } P72f: A2C2H2B-C12H9 + C2H2 -> A3-C14H10 + H { A = 2.62E+06 n = 2.00 E = 19.16 } # From A1 (x1/6) P73f: A2C2HA-C12H8 + C2H3 -> A3-C14H10 + H { A = 2.25E+16 n = -1.15 E = 61.01 } P74f: A2C2HB-C12H8 + C2H3 -> A3-C14H10 + H { A = 2.25E+16 n = -1.15 E = 61.01 } # From A1- P75f: A2C2HA*-C12H7 + C2H4 -> A3-C14H10 + H { A = 3.62E+28 n = -4.24 E = 99.85 } P76f: A2C2HB*-C12H7 + C2H4 -> A3-C14H10 + H { A = 3.62E+28 n = -4.24 E = 99.85 } # From A1- P77f: A2--C10H7 + C4H4 -> A3-C14H10 + H { A = 1.26E+04 n = 2.61 E = 6.00 } P78f: A2*-C10H7 + C4H4 -> A3-C14H10 + H { A = 1.26E+04 n = 2.61 E = 6.00 } # From A1 (x1/3) P79f: A3-C14H10 -> A3*-C14H9 + H { A = 4.30E+60 n =-12.48 E = 619.55 } P80f: A3-C14H10 + H -> A3*-C14H9 + H2 { A = 2.00E+08 n = 1.80 E = 68.42 } P81f: A3-C14H10 + OH -> A3*-C14H9 + H2O { A = 7.80E+03 n = 2.68 E = 3.07 } # From A1 (x2/3) P82f: A3-C14H10 -> A3--C14H9 + H { A = 8.60E+60 n =-12.48 E = 619.55 } P83f: A3-C14H10 + H -> A3--C14H9 + H2 { A = 4.01E+08 n = 1.80 E = 68.42 } P84f: A3-C14H10 + OH -> A3--C14H9 + H2O { A = 1.56E+04 n = 2.68 E = 3.07 } # Frenklach 2005 P85f: A3*-C14H9 -> A2R5--C12H7 + C2H2 { A = 1.30E+11 n = 1.08 E = 294.55 } # Acephenanthrylene # ----------------- # From A1C2H* P86f: A2R5C2H*-C14H7 + C2H2 -> A3R5--C16H9 { A = 1.34E+04 n = 2.50 E = 5.37 } # From A1C2H2 P87f: A2R5C2H2-C14H9 + C2H2 -> A3R5-C16H10 + H { A = 2.62E+06 n = 2.00 E = 19.16 } # From A2- P88f: A3--C14H9 + C2H2 -> A3R5-C16H10 + H { A = 2.81E+07 n = 1.77 E = 9.37 } # From A1- P89f: A2R5--C12H7 + C4H4 -> A3R5-C16H10 + H { A = 1.26E+04 n = 2.61 E = 6.00 } # From A1 (x1/3) P90f: A3R5-C16H10 -> A3R5--C16H9 + H { A = 2.15E+60 n =-12.48 E = 619.55 } P91f: A3R5-C16H10 + H -> A3R5--C16H9 + H2 { A = 2.01E+08 n = 1.80 E = 68.42 } P92f: A3R5-C16H10 + OH -> A3R5--C16H9 + H2O { A = 7.80E+03 n = 2.68 E = 3.07 } # Pyrene # ------ # From A2* P93f: A3*-C14H9 + C2H2 -> A4-C16H10 + H { A = 5.38E+07 n = 1.65 E = 10.71 } # From A1 (x4/3) P94f: A4-C16H10 -> A4--C16H9 + H { A = 1.72E+60 n =-12.48 E = 619.55 } P95f: A4-C16H10 + H -> A4--C16H9 + H2 { A = 8.03E+08 n = 1.80 E = 68.42 } P96f: A4-C16H10 + OH -> A4--C16H9 + H2O { A = 3.12E+04 n = 2.68 E = 3.07 } # Cyclopenta[cd]pyrene # -------------------- # From A2-/A2* P97f: A4--C16H9 + C2H2 -> A4R5-C18H10 + H { A = 2.81E+07 n = 1.77 E = 9.37 } P98f: A3R5--C16H9 + C2H2 -> A4R5-C18H10 + H { A = 5.38E+07 n = 1.65 E = 10.71 } # Fluoranthene # ------------ # From A1+A1- (x2/3 and x1) P99 : A2-C10H8 + A1--C6H5 -> FLTN-C16H10 + H2+H { A = 6.37E+11 n = .00 E = 9.07 } P100: A2--C10H7 + A1-C6H6 -> FLTN-C16H10 + H2+H { A = 9.55E+11 n = .00 E = 9.07 } # From A1-+A1- P101: A2--C10H7 + A1--C6H5 -> FLTN-C16H10 + 2H { A = 1.39E+13 n = .00 E = 0.47 } #==========================================================================# # # # Higher PAH Oxidation Chemistry # # Adapted from Benzene # # # #==========================================================================# # From A1-+O2 OX01 : A3*-C14H9 + O2 -> A2C2H2B-C12H9 + 2CO { A = 8.57E+20 n = -2.27 E = 30.08 } OX02 : A3--C14H9 + O2 -> A2C2H2A-C12H9 + 2CO { A = 8.57E+20 n = -2.27 E = 30.08 } OX03 : A4--C16H9 + O2 -> A3*-C14H9 + 2CO { A = 8.57E+20 n = -2.27 E = 30.08 } OX04 : A2R5--C12H7 + O2 -> A2--C10H7 + 2CO { A = 8.57E+20 n = -2.27 E = 30.08 } OX05 : 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 OX06 : A3-C14H10 + OH -> A2C2HA-C12H8 +CH3+CO { A = 1.10E+02 n = 3.25 E = 23.39 } OX07 : A3-C14H10 + OH -> A2C2HB-C12H8 +CH3+CO { A = 1.10E+02 n = 3.25 E = 23.39 } OX08 : A4-C16H10 + OH -> A3-C14H10 + HCCO { A = 2.20E+02 n = 3.25 E = 23.39 } OX09 : A2R5-C12H8 + OH -> A2-C10H8 + HCCO { A = 1.76E+02 n = 3.25 E = 23.39 } OX10 : A3R5-C16H10 + OH -> A3-C14H10 + HCCO { A = 2.20E+02 n = 3.25 E = 23.39 } OX11 : A4R5-C18H10 + OH -> A4-C16H10 + HCCO { A = 2.20E+02 n = 3.25 E = 23.39 } OX12 : FLTN-C16H10 + OH -> A3-C14H10 + HCCO { A = 2.20E+02 n = 3.25 E = 23.39 } #================================================================# # # # 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 = 0.0 [H2] + 0.0 [H2O] + 0.63 [AR] + 0.00 [CO2] + 1.0 [OTHER]. Let M2 = 2.5 [H2] + 12.0 [H2O] + 0.75 [AR] + 1.0 [OTHER]. Let M3 = 2.5 [H2] + 12.0 [H2O] + 0.00 [AR] + 1.0 [OTHER]. Let M4 = 1.5 [H2] + 11.7 [H2O] + 0.52 [AR] + 1.09 [CO] + 2.18 [CO2] + 0.89 [O2] + 1.0 [OTHER]. Let M5 = 3.0 [H2] + 0.0 [H2O] + 2.00 [N2] + 1.50 [O2] + 1.0 [OTHER]. Let M6 = 2.5 [H2] + 9.0 [H2O] + 1.50 [N2] + 1.0 [OTHER]. Let M7 = 2.0 [H2] + 12.0 [H2O] + 0.70 [AR] + 1.75 [CO] + 3.60 [CO2] + 1.0 [OTHER]. Let M8 = 2.0 [H2] + 0.0 [H2O] + 1.75 [CO] + 3.60 [CO2] + 1.0 [OTHER]. Let M9 = 2.0 [H2] + 6.0 [H2O] + 0.70 [AR] + 1.50 [CO] + 2.00 [CO2] + 2 [CH4] + 3 [C2H6] + 1.0 [OTHER].