--- CaltechMech.mech 2014/09/15 23:59:06 2.1 +++ CaltechMech.mech 2015/01/26 00:03:15 2.2 @@ -117,9 +117,10 @@ #=========================================================================# # # -# Chemistry of excited OH and CH states # -# de Vries, Hall, Simmons, Rickard, Kalitan, Petersen 2007 # -# (simplified) # +# Kinetics of Excited states compiled mostly from # +# Kathrotia, Fikri, Bozkurt, Hartmann, Riedel, Schulz - Comb. Flame 2010 # +# Bozkurt, Fiki, Schulz - Appl Phys B (2012) # +# (some rates reduced to collison limit) # # # #=========================================================================# @@ -127,26 +128,34 @@ # 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 } +# Reduced by 2 to match abs values +E01f: O + H + M10 -> S-OH + M10 { A = 3.00E+12 n = .00 E = 25.00 } +E02f: CH + O2 -> S-OH + CO { A = 8.00E+10 n = .00 E = .00 } + +E03f: S-OH -> OH { A = 1.45E+06 n = .00 E = .00 } +E04f: S-OH + AR -> OH + AR { A = 1.69E+12 n = .00 E = 17.32 } +E05f: S-OH + N2 -> OH + N2 { A = 1.08E+11 n = 0.50 E = -5.19 } +E06f: S-OH + O2 -> OH + O2 { A = 2.10E+12 n = 0.50 E = -2.02 } +E07f: S-OH + H2O -> OH + H2O { A = 1.55E+12 n = 0.50 E = -3.61 } +E08f: S-OH + CO -> OH + CO { A = 2.28E+12 n = 0.50 E = -3.30 } +E09f: S-OH + CO2 -> OH + CO2 { A = 1.61E+12 n = 0.50 E = -4.06 } # 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 } +E11f: C + H + M0 -> S-CH + M0 { A = 3.63E+13 n = .00 E = .00 } -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 } +# Devreindt, Peeters et al. 1997 +E12f: C2H + O -> S-CH + CO { A = 1.44E+13 n = .00 E = 1.91 } -# Elsamra, Vranckx, Carl 2005 -E11f: C2H + O2 -> S-CH + CO2 { A = 6.02E-04 n = 4.40 E = -9.56 } +E13f: S-CH -> CH { A = 1.86E+06 n = .00 E = .00 } +E14f: S-CH + AR -> CH + AR { A = 3.13E+11 n = .00 E = .00 } +E15f: S-CH + N2 -> CH + N2 { A = 3.03E+02 n = 3.40 E = -1.70 } +E16f: S-CH + O2 -> CH + O2 { A = 2.48E+06 n = 2.14 E = -7.20 } +E17f: S-CH + H2O -> CH + H2O { A = 5.30E+13 n = .00 E = .00 } +E18f: S-CH + CO -> CH + CO { A = 2.44E+12 n = 0.50 E = .00 } +E19f: S-CH + CO2 -> CH + CO2 { A = 2.40E-01 n = 4.30 E = -7.10 } @@ -193,101 +202,94 @@ 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 +# Ai reduced due to collision limit +G12f: T-CH2 + H + M9 -> CH3 + M9 { A = 1.04E+26 n = -2.76 E = 6.69 + Ai= 4.19E+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 } +G13f: T-CH2 + O -> HCO + H { A = 8.00E+13 n = .00 E = .00 } +G14f: T-CH2 + OH -> CH2O + H { A = 2.00E+13 n = .00 E = .00 } +G15f: T-CH2 + OH -> CH + H2O { A = 1.13E+07 n = 2.00 E = 12.55 } +G16f: 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 +G17f: T-CH2 + O2 -> HCO + OH { A = 9.57E+12 n = .00 E = 7.27 } +G18f: T-CH2 + O2 -> CH2O + O { A = 3.30E+12 n = .00 E = 7.27 } +G19f: T-CH2 + O2 -> CO2 + H2 { A = 3.63E+12 n = .00 E = 7.27 } + +G20f: T-CH2 + HO2 -> CH2O + OH { A = 2.00E+13 n = .00 E = .00 } +G21f: T-CH2 + C -> C2H + H { A = 5.00E+13 n = .00 E = .00 } +G22f: 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 } +G23f: T-CH2 + CH -> C2H2 + H { A = 4.00E+13 n = .00 E = .00 } +G24f: T-CH2 + T-CH2 -> C2H2 + H2 { A = 1.60E+15 n = .00 E = 49.97 } +G25 : 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 +G26f: S-CH2 + N2 -> T-CH2 + N2 { A = 1.50E+13 n = .00 E = 2.51 } +G27f: S-CH2 + AR -> T-CH2 + AR { A = 9.00E+12 n = .00 E = 2.51 } +G28f: S-CH2 + CO -> T-CH2 + CO { A = 9.00E+12 n = .00 E = .00 } +G29f: S-CH2 + CO2 -> T-CH2 + CO2 { A = 7.00E+12 n = .00 E = .00 } +G30f: S-CH2 + H2O -> T-CH2 + H2O { A = 3.00E+13 n = .00 E = .00 } + +G31f: S-CH2 + H -> CH + H2 { A = 3.00E+13 n = .00 E = .00 } +G32f: S-CH2 + O -> CO + H2 { A = 1.50E+13 n = .00 E = .00 } +G33f: S-CH2 + O -> HCO + H { A = 1.50E+13 n = .00 E = .00 } +G34f: S-CH2 + H2 -> CH3 + H { A = 7.00E+13 n = .00 E = .00 } +G35 : S-CH2 + O2 -> CO + OH + H { A = 2.80E+13 n = .00 E = .00 } +G36f: S-CH2 + O2 -> CO + H2O { A = 1.20E+13 n = .00 E = .00 } +G37f: S-CH2 + H2O + M9 -> CH3OH + M9 { A = 1.88E+38 n = -6.36 E = 21.09 Ai= 4.82E+17 ni= -1.16 Ei= 4.79 fcA = 0.3973 fctA = 208 fcb = 0.6027 fctb = 3922 fcc = 1.0 fctc = 10180 } -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 } +G38f: S-CH2 + OH -> CH2O + H { A = 3.00E+13 n = .00 E = .00 } +G39 : S-CH2 + H2O -> CH2O + H2 { A = 6.82E+10 n = .25 E = -3.91 } +G40f: 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 } +# Fridrichs, Davidson, Hanson 2004 +# k0 fitted to reproduce k(1atm) - Same Fc as before +G41f: CH2O + M9 -> HCO + H + M9 { A = 1.11E+40 n = -6.42 E = 420.33 + Ai= 8.36E+17 ni= -0.50 Ei= 373.00 + fcA = 0.2176 fctA = 271 + fcb = 0.7824 fctb = 2755 + fcc = 1.0 fctc = 6570 } +G42f: CH2O + M9 -> CO + H2 + M9 { A = 1.47E+45 n = -7.83 E = 405.10 + Ai= 1.23E+14 ni= .00 Ei= 347.00 + fcA = 0.068 fctA = 197 + fcb = 0.932 fctb = 1540 + fcc = 1.0 fctc = 10300 } + +# Wang, Dames, Davidson, Hanson 2014 +G43f: CH2O + H -> HCO + H2 { A = 5.86E+03 n = 3.13 E = 6.34 } -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 } +# Xu, Zhu, Lin 2006 +G44f: CH2O + OH -> HCO + H2O { A = 1.94E+06 n = 2.11 E = -7.06 } -G50f: CH2O + CH -> CH2CO + H { A = 9.46E+13 n = .00 E = -2.16 } +G45f: CH2O + O -> HCO + OH { A = 3.90E+13 n = .00 E = 14.81 } +G46f: CH2O + O2 -> HCO + HO2 { A = 1.00E+14 n = .00 E = 167.36 } +G47f: CH2O + HO2 -> HCO + H2O2 { A = 5.60E+06 n = 2.00 E = 50.21 } + +# Nguyen, Nguyen, Nguyen, Hoang, Vereecken 2014 +# (reduced due to collision limit) +G48f: CH2O + CH -> CH2CO + H { A = 2.68E+14 n = -0.32 E = -3.21 } # Methyl radical @@ -295,7 +297,7 @@ # Golden 2013 # Baulch et al.; Troe Ushakov -G51f: CH3 + H + M9 -> CH4 + M9 { A = 2.79E+34 n = -5.10 E = 11.65 +G49f: 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 @@ -303,48 +305,60 @@ # Harding, Klippenstein, Georgievskii 2005 # Reactions lumped - Products changed -G52f: CH3 + O -> CH2O + H { A = 5.54E+13 n = 0.05 E = -0.57 } +G50f: 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 +G51f: 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 } +G52f: CH3 + OH -> T-CH2 + H2O { A = 5.60E+07 n = 1.60 E = 22.68 } +G53f: CH3 + OH -> S-CH2 + H2O { A = 6.44E+17 n = -1.34 E = 5.93 } +G54: 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 +G55f: CH3 + O2 -> CH3O + O { A = 1.38E+13 n = .00 E = 127.70 } +G56f: CH3 + O2 -> CH2O + OH { A = 5.87E+11 n = .00 E = 57.91 } +G57f: 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 } +G58f: CH3O2 + CH3 -> CH3O + CH3O { A = 1.00E+13 n = .00 E = -5.02 } +G59 : CH3O2 + CH3O2 -> CH3O + CH3O + O2 { A = 1.40E+16 n = -1.61 E = 7.78 } +G60 : CH3O2 + HO2 -> CH3O + OH + O2 { A = 2.47E+11 n = .00 E = -6.57 } +G61 : 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 } +G62f: CH3 + HO2 -> CH3O + OH { A = 1.00E+12 n = 0.29 E = -2.87 } +G63f: 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 } +G64f: CH3 + H2O2 -> CH4 + HO2 { A = 2.45E+04 n = 2.47 E = 21.67 } +G65f: CH3 + HCO -> CH4 + CO { A = 2.65E+13 n = .00 E = .00 } +G66f: CH3 + CH2O -> CH4 + HCO { A = 3.32E+03 n = 2.81 E = 24.52 } + +G67f: CH3 + C -> C2H2 + H { A = 5.00E+13 n = .00 E = .00 } +G68f: CH3 + CH -> C2H3 + H { A = 3.00E+13 n = .00 E = .00 } +G69f: CH3 + T-CH2 -> C2H4 + H { A = 1.00E+14 n = .00 E = .00 } +G70f: CH3 + S-CH2 -> C2H4 + H { A = 1.20E+13 n = .00 E = -2.39 } +G71f: CH3 + CH3 -> C2H5 + H { A = 6.84E+12 n = 0.10 E = 44.35 } # Methoxy radical # --------------- +# Dames & Golden 2013 +G72f: 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 } +G73f: 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 } + 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 @@ -420,18 +434,19 @@ # 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 } +# Chikan, Leone 2005 +G113 : HCCO + O -> HCO + CO { A = 7.83E+13 n = .00 E = .00 } +G114 : HCCO + O -> CO2 + CH { A = 4.82E+12 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 } +# Assumed decomposition of HCOH into HCO+H +G115 : HCCO + OH -> CO + HCO + H { A = 2.62E+15 n = -0.41 E = 4.21 } G116f: HCCO + OH -> T-CH2 + CO2 { A = 8.97E+04 n = 2.09 E = -9.19 } # Klippenstein, Miller, Harding 2002 @@ -444,7 +459,7 @@ # Miller & Klippenstein 2004 # Refitted TROE form -G119f: C2H2 + H + M9 -> C2H3 + M9 { A = 6.34E+31 n = -4.66 E = 15.82 +G119f: C2H2 + H + M9 -> C2H3 + M9 { A = 9.06E+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 @@ -480,8 +495,8 @@ 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 } +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 } @@ -490,7 +505,7 @@ 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 } +G137f: CH2CO + O -> T-CH2 + CO2 { A = 1.75E+12 n = .00 E = 5.65 } # Vinyl radical @@ -504,7 +519,7 @@ 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 } +G140f: C2H3 + O -> CH3 + CO { 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 } @@ -512,85 +527,98 @@ # 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 } +# Oguchi, Sato, Matsui 2009 +# Matsugi, Miyoshi 2014 +G144f: C2H3 + O2 -> CH2CHO + O { A = 3.80E+11 n = 0.19 E = 0.20 } +G145f: C2H3 + O2 -> CH2O + HCO { A = 4.05E+17 n = -1.86 E = 4.88 } +G146 : C2H3 + O2 -> CH2O + CO + H { A = 2.22E+16 n = -1.35 E = 3.28 } -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 } +G147f: C2H3 + H2O2 -> C2H4 + HO2 { A = 1.21E+10 n = .00 E = -2.49 } +G148f: 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 } +G149f: CH2CHO -> CH2CO + H { A = 1.32E+34 n = -6.57 E = 202.45 } +G150f: 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 } +G151f: 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 } +G152 : CH2CHO + O2 -> CH2O + CO + OH { A = 1.81E+10 n = .00 E = 0.00 } +G153 : CH2CHO + O2 -> 2 HCO + OH { A = 2.35E+10 n = .00 E = 0.00 } +G154f: CH2CHO + H -> CH2CO + H2 { A = 1.10E+13 n = .00 E = 0.00 } +G155f: CH2CHO + OH -> CH2CO + H2O { A = 1.20E+13 n = .00 E = 0.00 } + +G156f: CH2CHO + H -> CH3 + HCO { A = 2.20E+13 n = .00 E = 0.00 } +G157f: CH2CHO + OH -> CH2OH + HCO { A = 3.01E+13 n = .00 E = 0.00 } +G158f: 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 } +# Mendes, Zhou, Curran 2014 +# (O/O2 rates as before/CH2O) +# (OH rate from CH2O x 0.5) + +# Sivaramakrishnan, Michael, Klippenstein 2010 +G159f: CH3CHO + M9 -> CH3 + HCO + M9 { A = 1.63E+59 n =-11.34 E = 401.32 + Ai= 2.72E+22 ni= -1.74 Ei= 361.33 + fcA = 0.0 fctA = 1 + fcb = 0.0 fctb = 1 + fcc = 0.138 fctc = -670 } +G160 : CH3CHO + H -> CH3 + CO + H2 { A = 1.31E+05 n = 2.58 E = 5.10 } +G161f: CH3CHO + H -> CH2CHO + H2 { A = 2.72E+03 n = 3.10 E = 21.78 } + +G162 : CH3CHO + O -> CH3 + CO + OH { A = 1.95E+13 n = .00 E = 14.81 } +G163 : CH3CHO + OH -> CH3 + CO + H2O { A = 9.70E+05 n = 2.11 E = -7.06 } +G164 : CH3CHO + O2 -> CH3 + CO + HO2 { A = 5.00E+13 n = .00 E = 167.36 } +G165 : CH3CHO + HO2 -> CH3 + CO + H2O2 { A = 2.78E-03 n = 4.50 E = 20.20 } +G166 : CH3CHO + CH3 -> CH3 + CO + CH4 { A = 1.55E+00 n = 3.70 E = 19.10 } + +G167f: CH3CHO + O -> CH2CHO + OH { A = 2.92E+12 n = .00 E = 7.57 } +G168f: CH3CHO + OH -> CH2CHO + H2O { A = 6.06E-01 n = 3.90 E = -4.47 } +G169f: CH3CHO + HO2 -> CH2CHO + H2O2 { A = 5.43E-02 n = 4.10 E = 78.02 } +G170f: CH3CHO + CH3 -> CH2CHO + CH4 { A = 1.44E+00 n = 3.70 E = 37.06 } # Ethylene # -------- # Ren, Davidson, Hanson 2012 -G167f: C2H4 + M9 -> H2C2 + H2 + M9 { A = 2.60E+16 n = .00 E = 283.76 } +G171 : C2H4 + M9 -> H2C2 + H2 + M9 { A = 3.71E+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 +G172f: C2H4 + H + M9 -> C2H5 + M9 { A = 2.89E+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 } +# Tautermann, Wellenzohn, Clary 2006 (written as reversed) +# 10% larger than Huynh, Panasewicz, Ratkiewicz, Truong 2007 +# Close to the recommendation of Baulch et al. 2005 +G173f: C2H4 + H -> C2H3 + H2 { A = 1.16E+07 n = 2.23 E = 55.80 } # 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 } +G174f: C2H4 + O -> CH2CHO + H { A = 7.66E+09 n = 0.88 E = 4.77 } +G175f: C2H4 + O -> T-CH2 + CH2O { A = 7.15E+04 n = 2.47 E = 3.89 } +G176f: 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 } +G177f: 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 } +G178f: C2H4 + O2 -> C2H3 + HO2 { A = 4.22E+13 n = .00 E = 259.83 } +G179 : 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 } +G180f: 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 +G181f: 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 @@ -600,50 +628,50 @@ # Ethyl radical # ------------- -G178f: C2H5 + H + M9 -> C2H6 + M9 { A = 1.99E+41 n = -7.08 E = 27.97 +G182f: 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 } +G183f: 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 } +G184f: 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 } +G185f: 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 } +G186f: 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 } +G187f: 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 } +G188f: C2H5 + HCO -> C2H6 + CO { A = 1.20E+14 n = .00 E = .00 } +G189f: C2H5 + HO2 -> C2H6 + O2 { A = 3.00E+11 n = .00 E = .00 } +G190f: 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 +G191f: 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 } +G192f: 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 +G193f: 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 @@ -651,21 +679,21 @@ # Chakraborty, Zhao, Lin, & Truhlar 2006 # Fit 500-2000K -G190f: C2H6 + H -> C2H5 + H2 { A = 1.70E+05 n = 2.70 E = 24.02 } +G194f: 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 } +G195f: 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 } +G196f: 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 } +G197f: 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 } +G198f: 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 } +G199f: C2H6 + CH3 -> C2H5 + CH4 { A = 3.45E+01 n = 3.44 E = 43.47 } # Propyl radicals @@ -673,71 +701,71 @@ # Curran 2006 - HPL -G196f: C3H6 + H + M9 -> N-C3H7 + M9 { A = 6.26E+38 n = -6.66 E = 29.29 +G200f: 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 +G201f: 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 } +G202f: N-C3H7 + H -> C2H5 + CH3 { A = 3.70E+24 n = -2.92 E = 52.32 } +G203f: I-C3H7 + H -> C2H5 + CH3 { A = 1.40E+28 n = -3.94 E = 66.59 } +G204f: N-C3H7 + H -> C3H6 + H2 { A = 1.80E+12 n = .00 E = .00 } +G205f: I-C3H7 + H -> C3H6 + H2 { A = 3.20E+12 n = .00 E = .00 } +G206f: N-C3H7 + O -> C2H5 + CH2O { A = 9.60E+13 n = .00 E = .00 } +G207f: I-C3H7 + O -> CH3CHO + CH3 { A = 9.60E+13 n = .00 E = .00 } +G208f: N-C3H7 + OH -> C3H6 + H2O { A = 2.41E+13 n = .00 E = .00 } +G209f: 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 } +G210f: N-C3H7 + O2 -> C3H6 + HO2 { A = 3.70E+16 n = -1.63 E = 14.30 } +G211f: 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 } +G212f: 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 +G213f: 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 +G214f: 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 +G215f: 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 } +G216f: C3H8 + H -> N-C3H7 + H2 { A = 9.36E+07 n = 1.97 E = 34.31 } +G217f: 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 } +G218f: C3H8 + O -> N-C3H7 + OH { A = 1.90E+05 n = 2.68 E = 15.55 } +G219f: C3H8 + O -> I-C3H7 + OH { A = 4.76E+04 n = 2.71 E = 8.81 } # 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 } +G220f: C3H8 + OH -> N-C3H7 + H2O { A = 5.15E+03 n = 2.94 E = -1.75 } +G221f: 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 } +G222f: C3H8 + CH3 -> N-C3H7 + CH4 { A = 9.03E-01 n = 3.65 E = 29.93 } +G223f: C3H8 + CH3 -> I-C3H7 + CH4 { A = 1.51E+00 n = 3.46 E = 29.93 } +G224f: C3H8 + HO2 -> N-C3H7 + H2O2 { A = 4.76E+04 n = 2.55 E = 69.00 } +G225f: C3H8 + HO2 -> I-C3H7 + H2O2 { A = 9.63E+03 n = 2.60 E = 58.20 } @@ -753,7 +781,13 @@ # Propynylidene # ------------- -R005f: C3H2 + O -> C3H2O { A = 1.36E+14 n = .00 E = .00 } +# Nguyen, Mebel, Lin, Kaiser 2001 +# Loison, Bergeat 2008 (reduced to collision rate) +R004f: C2H2 + CH -> C3H2 + H { A = 1.89E+14 n = .00 E = .00 } + +# Boullart, Devriendt, Borns, Peeters 1996 +R005f: C3H2 + O -> C2H + HCO { 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 } @@ -771,12 +805,12 @@ 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 } +R014 : C3H2O + H -> C2H + CO + H2 { A = 1.31E+05 n = 2.58 E = 5.10 } +R015 : C3H2O + O -> C2H + CO + OH { A = 1.95E+13 n = .00 E = 14.81 } +R016 : C3H2O + OH -> C2H + CO + H2O { A = 9.10E+05 n = 2.11 E = -7.06 } +R017 : C3H2O + O2 -> C2H + CO + HO2 { A = 5.00E+13 n = .00 E = 167.36 } +R018 : C3H2O + HO2 -> C2H + CO + H2O2 { A = 2.78E-03 n = 4.50 E = 20.20 } +R019 : C3H2O + CH3 -> C2H + CO + CH4 { A = 1.55E+00 n = 3.70 E = 19.10 } # Propargyl radical @@ -869,16 +903,18 @@ # 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 } +R056f: A-C3H4 + CH3 -> C3H3 + CH4 { A = 2.06E-01 n = 3.94 E = 51.98 } 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 } +# Nguyen, Peeters & Vereecken 2006 - rate +# Leonori, Balucani et al. 2012 - products +R058f: A-C3H4 + O -> C2H4 + CO { A = 9.63E+06 n = 2.05 E = 0.75 } + +# Adapted from C2H2+O (half-half) +# Zhao, Wu, Zhao et al. 2009 - Products (singlet) +# Balucani, Leonori et al. 2014 - Products (triplet) +R059f: P-C3H4 + O -> C2H4 + CO { A = 1.85E+09 n = 1.28 E = 10.34 } +R959f: P-C3H4 + O -> HCCO + CH3 { A = 1.85E+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 } @@ -897,11 +933,11 @@ 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 } +R066 : C2H3CHO + H -> C2H3 + CO + H2 { A = 1.31E+05 n = 2.58 E = 5.10 } +R067 : C2H3CHO + O -> C2H3 + CO + OH { A = 1.95E+13 n = .00 E = 14.81 } +R068 : C2H3CHO + OH -> C2H3 + CO + H2O { A = 9.70E+05 n = 2.11 E = -7.06 } +R069 : C2H3CHO + HO2 -> C2H3 + CO + H2O2 { A = 2.78E-03 n = 4.50 E = 20.20 } +R070 : C2H3CHO + CH3 -> C2H3 + CO + CH4 { A = 1.55E+00 n = 3.70 E = 10.10 } # Allyl radicals @@ -1001,19 +1037,19 @@ 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 } +# Cavallotti, Leonori, Balucani et al. 2014 +# CH3CH replaced by C2H4 - 1bar +R120f: C3H6 + O -> CH2CHO + CH3 { A = 8.12E+08 n = 1.25 E = 2.26 } +R121f: C3H6 + O -> C2H4 + CH2O { A = 3.63E+10 n = 0.82 E = 7.65 } +R123f: C3H6 + O -> A-C3H5 + OH { A = 1.43E+02 n = 3.37 E = 0.73 } # 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 } +R126f: C3H6 + CH3 -> S-C3H5 + CH4 { A = 1.03E-01 n = 3.94 E = 51.98 } +R127f: C3H6 + CH3 -> T-C3H5 + CH4 { A = 5.15E-02 n = 3.94 E = 51.98 } # Hexadiyene @@ -1055,42 +1091,30 @@ # # #==========================================================================# - # 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 } +H02f: C4H2 -> C4H + H { A = 2.20E+14 n = .00 E = 487.85 } +H03f: C4H2 + H -> C4H + H2 { A = 2.00E+14 n = .00 E = 108.78 } # 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 } +H04f: C2H2 + C2H -> C4H2 + H { A = 7.80E+13 n = .00 E = .00 } # Klippenstein & Miller 2005 # Refitted Rate & TROE form -H08f: C4H2 + H + M9 -> I-C4H3 + M9 { Ai= 4.31E+10 ni= 1.16 Ei= 7.33 +H05f: 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 } +H06f: C4H2 + H -> N-C4H3 { A = 1.37E+39 n = -7.87 E = 64.61 } + +H07f: C4H2 + O -> C3H2 + CO { A = 2.80E+13 n = .00 E = 7.24 } +H08f: C4H2 + O -> C4H2O { A = 4.00E+13 n = .00 E = .00 } +H09f: C4H2 + O2 -> HCCO + HCCO { A = 9.56E+12 n = .00 E = 130.12 } # Senosiain, Klippenstein & Miller 2007 H10f: C4H2 + OH -> C4H + H2O { A = 9.15E+09 n = 1.03 E = 90.99 } @@ -1101,64 +1125,63 @@ # 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 } +H13f: C4H2O + H -> C2H2 + HCCO { A = 5.00E+13 n = .00 E = 12.55 } +H14f: C4H2O + O -> C3H2 + CO2 { A = 1.00E+13 n = .00 E = .00 } +H15f: C4H2O + OH -> CH2CO + HCCO { A = 1.00E+07 n = 2.00 E = 8.37 } # 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 } +# Wang 1992 ?? +H16f: N-C4H3 -> I-C4H3 { A = 4.10E+43 n = -9.50 E = 221.75 } +H17f: N-C4H3 + H -> I-C4H3 + H { A = 2.50E+20 n = -1.67 E = 45.19 } +H18f: N-C4H3 + H -> C4H4 { A = 2.00E+47 n =-10.26 E = 54.69 } +H19f: I-C4H3 + H -> C4H4 { A = 3.40E+43 n = -9.01 E = 50.71 } +H20f: N-C4H3 + H -> C2H2 + H2C2 { A = 6.30E+25 n = -3.34 E = 41.90 } +H21f: I-C4H3 + H -> C2H2 + H2C2 { A = 2.80E+23 n = -2.55 E = 45.10 } + +# From C2H3 +H22f: N-C4H3 + H -> C4H2 + H2 { A = 1.50E+13 n = .00 E = .00 } +H23f: I-C4H3 + H -> C4H2 + H2 { A = 3.00E+13 n = .00 E = .00 } +H24f: N-C4H3 + OH -> C4H2 + H2O { A = 2.50E+12 n = .00 E = .00 } +H25f: I-C4H3 + OH -> C4H2 + H2O { A = 5.00E+12 n = .00 E = .00 } +H26f: N-C4H3 + O2 -> C4H2 + HO2 { A = 6.70E+05 n = 1.61 E = -1.61 } +H27f: I-C4H3 + O2 -> C4H2 + HO2 { A = 1.34E+06 n = 1.61 E = -1.61 } + +H28f: N-C4H3 + O -> C2H2 + HCCO { A = 1.03E+13 n = 0.21 E = -1.79 } +H29f: I-C4H3 + O -> CH2CO + C2H { A = 2.00E+13 n = .00 E = .00 } +H30f: I-C4H3 + O2 -> HCCO + CH2CO { A = 1.63E+11 n = .00 E = -7.53 } # Vinylacetylene # -------------- +H31f: C4H4 -> C4H2 + H2 { A = 1.30E+15 n = .00 E = 396.14 } +H32f: C4H4 -> C2H2 + C2H2 { A = 3.40E+13 n = .00 E = 322.59 } + # 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 } +#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 } +H33f: 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 } +H34f: C4H4 + H -> N-C4H3 + H2 { A = 1.16E+07 n = 2.23 E = 55.80 } +H35f: C4H4 + H -> I-C4H3 + H2 { A = 5.80E+06 n = 2.23 E = 43.25 } +H36f: C4H4 + OH -> N-C4H3 + H2O { A = 2.23E+04 n = 2.75 E = 9.27 } +H37f: C4H4 + OH -> I-C4H3 + H2O { A = 1.12E+04 n = 2.75 E = -3.28 } +H38f: C4H4 + CH3 -> N-C4H3 + CH4 { A = 1.03E-01 n = 3.94 E = 51.98 } +H39f: C4H4 + CH3 -> I-C4H3 + CH4 { A = 5.15E-02 n = 3.94 E = 39.43 } -# 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 } +# From C2H4 +H40f: C4H4 + O -> C3H3 + HCO { A = 6.00E+08 n = 1.45 E = -3.60 } -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 } +# From C2H2 +#41f: C4H4 + OH -> CH2CO + C2H3 { A = 2.10E+01 n = 3.22 E = -1.76 } +H42f: C4H4 + OH -> A-C3H5 + CO { A = 1.28E+09 n = 0.73 E = 10.79 } # Hexatriyne & Octotetrayne @@ -1166,17 +1189,17 @@ # 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 } +H43f: C4H2 + C2H -> C6H2 + H { A = 7.80E+13 n = .00 E = .00 } +H44f: C2H2 + C4H -> C6H2 + H { A = 7.80E+13 n = .00 E = .00 } +H45f: C6H2 + C2H -> C8H2 + H { A = 7.80E+13 n = .00 E = .00 } +H46f: 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 } +H47f: 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 } +H48 : C6H2 + OH -> C4H2 + HCCO { A = 3.41E+10 n = 0.31 E = 5.00 } +H49 : C8H2 + OH -> C6H2 + HCCO { A = 3.41E+10 n = 0.31 E = 5.00 } @@ -1189,97 +1212,164 @@ #==========================================================================# -# Butadiene -# --------- +# 1,3-Butadiene +# ------------- -# Baulch et al. 2005 -# Full rate to addition -B01f: 2 C2H3 -> C4H6 { A = 8.43E+13 n = .00 E = .00 } +# Peukert, Naumann, Braun-unkhoff 2009 +B01f: C4H6 -> C2H4 + C2H2 { A = 7.00E+12 n = .00 E = 280.75 } -# 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 } +B02f: C2H3 + C2H3 -> C4H6 { A = 1.50E+42 n = -8.84 E = 52.23 } -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 } +# Ismail, Georgievskii, Taatjes, et al. 2007 +# Rate fitted at 1.33bar +B03f: C2H4 + C2H3 -> C4H6 + H { A = 2.15E+12 n = 0.46 E = 62.65 } 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 } +#B05f: C4H6 + H -> P-C3H4 + CH3 { A = 2.00E+12 n = .00 E = 29.29 } +#B06f: C4H6 + H -> A-C3H4 + CH3 { A = 2.00E+12 n = .00 E = 29.29 } -# 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 +# Adapted from C2H4 # 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 } +# Rate for O refitted - 8e11 backward +B10f: C4H6 + H -> N-C4H5 + H2 { A = 1.16E+07 n = 2.23 E = 55.80 } +B11f: C4H6 + O -> N-C4H5 + OH { A = 7.12E+14 n = -0.23 E = 41.03 } +B12f: C4H6 + OH -> N-C4H5 + H2O { A = 1.56E+05 n = 2.46 E = 7.78 } +B13f: C4H6 + O2 -> N-C4H5 + HO2 { A = 4.22E+13 n = .00 E = 259.83 } 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 } +B15f: C4H6 + HO2 -> N-C4H5 + H2O2 { A = 1.66E+10 n = 0.36 E = 95.13 } -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 } +# Adapted from C2H4 - 3kcal +B16f: C4H6 + H -> I-C4H5 + H2 { A = 5.80E+06 n = 2.23 E = 43.25 } +B17f: C4H6 + O -> I-C4H5 + OH { A = 3.56E+14 n = -0.23 E = 28.48 } +B18f: C4H6 + OH -> I-C4H5 + H2O { A = 2.17E+06 n = 2.08 E = 6.58 } +B19f: C4H6 + O2 -> I-C4H5 + HO2 { A = 2.11E+13 n = .00 E = 247.28 } +B20f: C4H6 + CH3 -> I-C4H5 + CH4 { A = 1.03E-01 n = 3.94 E = 39.43 } +B21f: C4H6 + HO2 -> I-C4H5 + H2O2 { A = 8.31E+09 n = 0.36 E = 82.58 } + +# From C3H6 + O (x2) +# Cavallotti, Leonori, Balucani et al. 2014 +B22f: C4H6 + O -> CH2CHO + C2H3 { A = 1.62E+09 n = 1.25 E = 2.26 } +B23f: C4H6 + O -> A-C3H4 + CH2O { A = 7.26E+10 n = 0.82 E = 7.65 } -# 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 } +# From C2H4+O2 +B25 : C4H6 + O2 -> A-C3H5 + CO2 + H { A = 4.90E+12 n = 0.42 E = 317.15 } -# Butadienyl radicals -# ------------------- +# 1,2-Butadiene +# ------------- -# Wang & Frenklach 1994 -B21f: C2H3 + C2H2 -> N-C4H5 { A = 9.30E+38 n = -8.76 E = 50.21 } +B26f: D-C4H6 -> C4H6 { A = 3.00E+13 n = .00 E = 271.96 } +B27f: D-C4H6 + H -> C4H6 + H { A = 2.00E+13 n = .00 E = 16.74 } -# 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 } +# HPL from Knyazev & Slagle 2001 +B28f: C3H3 + CH3 + M9 -> D-C4H6 + M9 { A = 2.60E+57 n =-11.94 E = 40.89 + Ai= 4.09E+13 ni= .00 Ei= -1.08 + fcA = 0.825 fctA = 1341 + fcb = 0.175 fctb = 60000 + fcc = 1.0 fctc = 9770 } -# Wang & Frenklach 1997 -B28f: N-C4H5 + H -> I-C4H5 + H { A = 3.10E+26 n = -3.35 E = 72.90 } +# Revised using C3H6+H->C2H4+CH3 +B29f: D-C4H6 + H -> A-C3H4 + CH3 { A = 2.67E+12 n = 0.47 E = 22.72 } +# Revised using A-C3H4+H->P-C3H4+H +B30f: D-C4H6 + H -> P-C3H4 + CH3 { A = 2.55E+18 n = -1.09 E = 47.84 } + +# Revised based on C3H6+R +B31f: D-C4H6 -> I-C4H5 + H { A = 1.91E+54 n =-11.28 E = 464.83 } +B32f: D-C4H6 + H -> I-C4H5 + H2 { A = 1.42E+04 n = 2.82 E = 14.23 } +B33f: D-C4H6 + O -> I-C4H5 + OH { A = 9.50E+04 n = 2.68 E = 15.55 } +B34f: D-C4H6 + OH -> I-C4H5 + H2O { A = 9.00E+04 n = 2.59 E = 1.74 } +B35f: D-C4H6 + O2 -> I-C4H5 + HO2 { A = 1.17E+12 n = 0.41 E = 162.33 } +B36f: D-C4H6 + CH3 -> I-C4H5 + CH4 { A = 7.00E+13 n = .00 E = 77.40 } + +# From A-C3H4+R +B37f: D-C4H6 + M0 -> S-C4H5 + H + M0 { A = 5.38E+42 n = -6.81 E = 420.61 } +B38f: D-C4H6 + H -> S-C4H5 + H2 { A = 1.16E+07 n = 2.23 E = 55.80 } +B39f: D-C4H6 + OH -> S-C4H5 + H2O { A = 2.23E+04 n = 2.75 E = 9.27 } +B40f: D-C4H6 + CH3 -> S-C4H5 + CH4 { A = 2.06E-01 n = 3.94 E = 51.98 } -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 A-C3H4 + O +B41f: D-C4H6 + O -> C3H6 + CO { A = 9.63E+06 n = 2.05 E = 0.75 } -# 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 } +# 2-Butyne +# -------- -# From C2H5 + O -B45f: I-C4H5 + O -> C3H3 + CH2O { A = 3.17E+13 n = 0.03 E = -1.65 } +B42f: S-C4H6 -> C4H6 { A = 3.00E+13 n = .00 E = 271.96 } +B43f: S-C4H6 -> D-C4H6 { A = 3.00E+13 n = .00 E = 280.33 } +B44f: S-C4H6 + H -> D-C4H6 + H { A = 2.00E+13 n = .00 E = 16.74 } + +# Revised using P-C3H4+H->C2H2+CH3 +B45f: S-C4H6 + H -> P-C3H4 + CH3 { A = 1.39E+16 n = -0.36 E = 36.11 } + +# Peukert, Naumann, Braun-unkhoff 2009 +B46f: S-C4H6 -> S-C4H5 + H { A = 3.80E+15 n = .00 E = 373.21 } + +# Revised based on C2H6+R +B47f: S-C4H6 + H -> S-C4H5 + H2 { A = 1.70E+05 n = 2.70 E = 24.02 } +B48f: S-C4H6 + O -> S-C4H5 + OH { A = 3.17E+01 n = 3.80 E = 13.10 } +B49f: S-C4H6 + OH -> S-C4H5 + H2O { A = 1.61E+06 n = 2.22 E = 3.10 } +B50f: S-C4H6 + CH3 -> S-C4H5 + CH4 { A = 3.45E+01 n = 3.44 E = 43.47 } + +# From C2H2 - Total rate +#B51 : S-C4H6 + O -> C2H3 + CO + CH3 { A = 3.70E+09 n = 1.28 E = 10.34 } +B52 : S-C4H6 + OH -> C2H4 + CO + CH3 { A = 1.86E+03 n = 2.67 E = 0.97 } -B46f: N-C4H5 + C2H3 -> A1-C6H6 + H2 { A = 1.84E-13 n = 7.07 E = -15.11 } + +# Butadienyl radicals +# ------------------- + +B53f: C2H3 + C2H2 -> N-C4H5 { A = 9.30E+38 n = -8.76 E = 50.21 } +B54f: C2H3 + C2H2 -> I-C4H5 { A = 1.60E+46 n =-10.98 E = 77.82 } + +B55f: C2H3 + C2H3 -> I-C4H5 + H { A = 1.20E+22 n = -2.44 E = 57.13 } +B56f: C2H3 + C2H3 -> N-C4H5 + H { A = 2.40E+20 n = -2.04 E = 64.28 } + +B57f: C4H4 + H -> N-C4H5 { A = 1.30E+51 n =-11.92 E = 69.04 } +B58f: C4H4 + H -> I-C4H5 { A = 4.90E+51 n =-11.92 E = 74.06 } + +B59f: N-C4H5 -> I-C4H5 { A = 1.50E+67 n =-16.89 E = 247.27 } +B60f: N-C4H5 + H -> I-C4H5 + H { A = 3.10E+26 n = -3.35 E = 72.90 } + +B61f: N-C4H5 + H -> C4H4 + H2 { A = 1.50E+13 n = .00 E = .00 } +B62f: N-C4H5 + OH -> C4H4 + H2O { A = 2.50E+12 n = .00 E = .00 } +B63f: N-C4H5 + O2 -> C4H4 + HO2 { A = 6.70E+05 n = 1.61 E = -1.61 } +B64f: N-C4H5 + CH3 -> C4H4 + CH4 { A = 4.52E+12 n = .00 E = -3.20 } + +# From C2H3 +B66f: N-C4H5 + O -> A-C3H5 + CO { A = 1.03E+13 n = 0.21 E = -1.79 } +B67 : N-C4H5 + O2 -> A-C3H5 + CO + O { A = 3.80E+11 n = 0.19 E = 0.20 } +B68f: N-C4H5 + O2 -> C2H3CHO + HCO { A = 4.05E+17 n = -1.86 E = 4.88 } +B69 : N-C4H5 + O2 -> C2H3CHO + CO + H { A = 2.22E+16 n = -1.35 E = 3.28 } + +B70f: I-C4H5 + H -> C3H3 + CH3 { A = 2.00E+13 n = .00 E = 8.37 } + +B71f: I-C4H5 + H -> C4H4 + H2 { A = 3.00E+13 n = .00 E = .00 } +B72f: I-C4H5 + OH -> C4H4 + H2O { A = 5.00E+12 n = .00 E = .00 } +B73f: I-C4H5 + O2 -> C4H4 + HO2 { A = 1.34E+06 n = 1.61 E = -1.61 } +B74f: I-C4H5 + CH3 -> C4H4 + CH4 { A = 9.04E+12 n = .00 E = -3.20 } + +# From A-C3H5 +B75f: I-C4H5 + O -> CH2CO + C2H3 { A = 3.17E+13 n = 0.03 E = -1.65 } +B76 : I-C4H5 + O2 -> CH2CO + C2H2 + OH { A = 9.71E+20 n = -2.70 E = 104.52 } +B77f: I-C4H5 + O2 -> CH2CO + CH2CHO { A = 3.08E+09 n = 0.37 E = 70.75 } +B78 : I-C4H5 + HO2 -> CH2CO + C2H3 + OH { A = 1.19E+09 n = 1.03 E = -9.41 } + +B79f: S-C4H5 -> I-C4H5 { A = 1.50E+67 n =-16.89 E = 247.27 } +B80f: S-C4H5 + H -> I-C4H5 + H { A = 3.10E+26 n = -3.35 E = 72.90 } + +# From C3H3 +#81 : S-C4H5 + O -> C3H2O + CH3 { A = 1.38E+14 n = .00 E = .00 } +B82 : S-C4H5 + O2 -> CH2CO + CH3 + CO { A = 1.70E+05 n = 1.70 E = 6.28 } +B83 : S-C4H5 + HO2 -> C2H2 + CH3 + CO + OH { A = 8.00E+11 n = .00 E = .00 } + +# From C3H3+C3H3 +B84f: S-C4H5 + C3H3 -> A1CH3-C7H8 { A = 1.87E+46 n = -9.84 E = 70.31 } +B85f: S-C4H5 + C3H3 -> A1CH3*-C7H7 + H { A = 5.77E+37 n = -7.00 E = 131.82 } @@ -1336,7 +1426,7 @@ # ---------------------- 5 Species ----------------------- # # -------------------- 11 Reactions ---------------------- # -/* Commented for now +/* Commented for now */ # Formation of ROO @@ -1365,7 +1455,7 @@ # all products lumped HX30: C6H12O + OH -> N-C4H9 + CH2CO + H2O { A = 3.68E+12 n = .00 E = .00 } -*/ +/**/ #==========================================================================# @@ -1468,6 +1558,7 @@ # # #==========================================================================# + # 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 @@ -1546,7 +1637,7 @@ # -------------------- LOW TEMPERATURE -------------------- # # ----------------------- 10 Species ---------------------- # # ---------------------- 21 Reactions --------------------- # -/* +/**/ # Reactions of C12H25O2 # Backward rate reduced (x1/6) # to mimic lumping of peroxy species @@ -1596,7 +1687,7 @@ 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 } -*/ +/**/ @@ -1621,6 +1712,8 @@ # 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 } +# N-alkene decomposition from Manion & Awan 2015 +# { A = 3.39E+15 n = .00 E = 302.40 } # Decyl radical @@ -1633,7 +1726,7 @@ # Reactions of C10H20 -NC03 : C10H20 -> N-C7H15 + A-C3H5 { A = 1.00E+16 n = .00 E = 297.06 } +NC03 : C10H20 -> N-C7H15 + A-C3H5 { A = 3.39E+15 n = .00 E = 302.40 } 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 } @@ -1659,7 +1752,7 @@ # Reactions of C9H18 -NC15 : C9H18 -> N-C6H13 + A-C3H5 { A = 1.00E+16 n = .00 E = 297.06 } +NC15 : C9H18 -> N-C6H13 + A-C3H5 { A = 3.39E+15 n = .00 E = 302.40 } 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 } @@ -1684,7 +1777,7 @@ # Reactions of C8H16 -NC26 : C8H16 -> N-C5H11 + A-C3H5 { A = 1.00E+16 n = .00 E = 297.06 } +NC26 : C8H16 -> N-C5H11 + A-C3H5 { A = 3.39E+15 n = .00 E = 302.40 } 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 } @@ -1708,7 +1801,7 @@ # Reactions of C7H14 -NC36 : C7H14 -> N-C4H9 + A-C3H5 { A = 1.00E+16 n = .00 E = 297.06 } +NC36 : C7H14 -> N-C4H9 + A-C3H5 { A = 3.39E+15 n = .00 E = 302.40 } 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 } @@ -1754,7 +1847,7 @@ # Reactions of C5H10 -NC54 : C5H10 -> A-C3H5 + C2H5 { A = 1.00E+16 n = .00 E = 297.06 } +NC54 : C5H10 -> A-C3H5 + C2H5 { A = 3.39E+15 n = .00 E = 302.40 } 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 } @@ -1775,22 +1868,25 @@ # Reactions of C4H8 reactions -NC61 : C4H8 -> A-C3H5 + CH3 { A = 1.00E+16 n = .00 E = 297.06 } +# Manion, Awan 2015 +NC61 : C4H8 -> A-C3H5 + CH3 { A = 3.39E+15 n = .00 E = 302.40 } +NC62 : C4H8 + H -> C3H6 + CH3 { A = 1.05E+09 n = 1.40 E = 3.04 } +NC63 : C4H8 + H -> C2H5 + C2H4 { A = 9.02E+08 n = 1.40 E = 9.66 } -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 } +NC64 : C4H8 + H -> C4H7 + H2 { A = 3.70E+13 n = .00 E = 16.32 } +NC65 : 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 -> C2H4 + C2H3 { A = 1.00E+11 n = .00 E = 154.81 } +NC67 : 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 } +NC68 : C4H7 + H -> C4H6 + H2 { A = 3.16E+13 n = .00 E = .00 } +NC69 : C4H7 + O2 -> C4H6 + HO2 { A = 1.00E+09 n = .00 E = .00 } +NC70 : 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 } +NC71 : C4H7 + HO2 -> A-C3H5 + CH2O + OH { A = 7.00E+12 n = .00 E = -4.18 } +NC72 : C4H7 + CH3O2 -> A-C3H5 + CH2O + CH3O { A = 7.00E+12 n = .00 E = -4.18 } @@ -1848,7 +1944,7 @@ 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 } +IC24 : Y-C7H14 + OH -> X-C7H13 + H2O { A = 6.46E-09 n = 6.18 E = -41.33 } # Reactions of X-C7H13 @@ -2246,15 +2342,15 @@ # Benzaldehyde # ------------ -# From CH3CHO - Baulch et al. 2005 +# From CH3CHO # 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 } +T31 : A1CHO-C7H6O -> A1--C6H5 + CO + H { A = 2.72E+22 n = -1.74 E = 361.33 } # 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 } +T32 : A1CHO-C7H6O + H -> A1--C6H5 + CO + H2 { A = 1.31E+05 n = 2.58 E = 5.10 } +T33 : A1CHO-C7H6O + O -> A1--C6H5 + CO + OH { A = 1.95E+13 n = .00 E = 14.81 } +T34 : A1CHO-C7H6O + OH -> A1--C6H5 + CO + H2O { A = 9.70E+05 n = 2.11 E = -7.06 } +T35 : A1CHO-C7H6O + CH3 -> A1--C6H5 + CO + CH4 { A = 1.55E+00 n = 3.70 E = 19.10 } # Cresol @@ -2358,8 +2454,9 @@ 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 } +ST24 : A1C2H2-C8H7 + O2 -> A1CH2-C7H7 + CO + O { A = 3.80E+11 n = 0.19 E = 0.20 } +ST25f: A1C2H2-C8H7 + O2 -> A1CHO-C7H6O + HCO { A = 4.05E+17 n = -1.86 E = 4.88 } +ST26 : A1C2H2-C8H7 + O2 -> A1CHO-C7H6O + CO + H { A = 2.22E+16 n = -1.35 E = 3.28 } # Ethynylbenzene @@ -2367,18 +2464,18 @@ # Goulay & Leone 2006 # Woon, Park & Jin-Young 2009 -ST26f: A1-C6H6 + C2H -> A1C2H-C8H6 + H { A = 2.00E+14 n = .00 E = .00 } +ST27f: 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 } +ST28f: A1C2H-C8H6 -> A1C2H*-C8H5 + H { A = 4.30E+60 n =-12.48 E = 619.59 } +ST29f: A1C2H-C8H6 + H -> A1C2H*-C8H5 + H2 { A = 2.01E+08 n = 1.80 E = 68.42 } +ST30f: 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 + 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 } +ST32f: A1C2H-C8H6 + OH -> A1--C6H5 + CH2CO { A = 2.10E+01 n = 3.22 E = -1.76 } +ST33f: A1C2H-C8H6 + OH -> A1CH2-C7H7 + CO { A = 6.40E+08 n = 0.73 E = 10.79 } @@ -2421,18 +2518,19 @@ 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 } +# From N-C3H7 +EB13f: A1C2H4-C8H9 + O -> A1CH2-C7H7 + CH2O { A = 9.60E+13 n = .00 E = .00 } + +# From N-C3H7 +EB14f: A1C2H4-C8H9 + H -> A1C2H3-C8H8 + H2 { A = 1.80E+12 n = .00 E = .00 } +EB15f: A1C2H4-C8H9 + OH -> A1C2H3-C8H8 + H2O { A = 2.41E+13 n = .00 E = .00 } 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 } +# Altarawneh, Dlugogorski, Kennedy, Mackie 2013 +EB17f: A1C2H4-C8H9 + O2 -> A1C2H3-C8H8 + HO2 { A = 3.08E+13 n = .00 E = 75.66 } # 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 } - +EB18 : A1C2H4-C8H9 + HO2 -> A1CH2-C7H7 + CH2O + OH{ A = 7.00E+12 n = .00 E = -4.18 } #=========================================================================# @@ -2497,10 +2595,10 @@ # Tolualdehyde # ------------ -# From A1CH3 & A1CHO decomposition +# From A1CH3 & CH3CHO 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 } +XY23 : A1CH3CHO-C8H8O -> A1CH3*-C7H7 + CO + H { A = 2.72E+22 n = -1.74 E = 361.33 } # From A1CH3+R XY24f: A1CH3CHO-C8H8O + H -> A1CHOCH2-C8H7O + H2 { A = 6.47E+00 n = 3.98 E = 14.16 } @@ -2508,11 +2606,11 @@ 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 } +# From CH3CHO+R +XY28 : A1CH3CHO-C8H8O + H -> A1CH3*-C7H7 + CO + H2 { A = 1.31E+05 n = 2.58 E = 5.10 } +XY29 : A1CH3CHO-C8H8O + O -> A1CH3*-C7H7 + CO + OH { A = 1.95E+13 n = .00 E = 14.81 } +XY30 : A1CH3CHO-C8H8O + OH -> A1CH3*-C7H7 + CO + H2O { A = 9.70E+05 n = 2.11 E = -7.06 } +XY31 : A1CH3CHO-C8H8O + CH3 -> A1CH3*-C7H7 + CO + CH4 { A = 1.55E+00 n = 3.70 E = 19.10 } # Tolualdehyde radical @@ -2530,14 +2628,14 @@ # Phthalaldehyde # -------------- -# From A1CHO decomposition (x2) -XY34 : A1CHOCHO-C8H6O2 -> A1--C6H5 + 2 CO + H { A = 4.20E+16 n = .00 E = 342.00 } +# From CH3CHO decomposition (x2) +XY34 : A1CHOCHO-C8H6O2 -> A1--C6H5 + 2 CO + H { A = 5.44E+22 n = -1.74 E = 361.33 } -# 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 } +# From CH3CHO+R (x2) +XY35 : A1CHOCHO-C8H6O2 + H -> A1CHO-C7H6O + CO + H { A = 2.62E+05 n = 2.58 E = 5.10 } +XY36 : A1CHOCHO-C8H6O2 + O -> A1CHO-C7H6O + CO + O { A = 3.90E+13 n = .00 E = 14.81 } +XY37 : A1CHOCHO-C8H6O2 + OH -> A1CHO-C7H6O + CO + OH { A = 1.94E+06 n = 2.11 E = -7.06 } +XY38 : A1CHOCHO-C8H6O2 + CH3 -> A1CHO-C7H6O + CO + CH3 { A = 3.10E+00 n = 3.70 E = 19.10 } @@ -2729,12 +2827,12 @@ # Naphthaldehyde # -------------- -MN26 : A2CHO-C11H8O -> A2--C10H7 + CO + H { A = 2.10E+16 n = .00 E = 342.00 } +MN26 : A2CHO-C11H8O -> A2--C10H7 + CO + H { A = 2.72E+22 n = -1.74 E = 361.33 } -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 } +MN27 : A2CHO-C11H8O + H -> A2--C10H7 + CO +H2 { A = 1.31E+05 n = 2.58 E = 5.10 } +MN28 : A2CHO-C11H8O + O -> A2--C10H7 + CO +OH { A = 1.95E+13 n = .00 E = 14.81 } +MN29 : A2CHO-C11H8O + OH -> A2--C10H7 + CO +H2O { A = 9.70E+05 n = 2.11 E = -7.06 } +MN30 : A2CHO-C11H8O + CH3-> A2--C10H7 + CO +CH4 { A = 1.55E+00 n = 3.70 E = 19.10 } @@ -2888,7 +2986,6 @@ # 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 } @@ -2906,7 +3003,6 @@ # Phenanthrene # ------------ - # From A1C2H3* P63f: P2--C12H9 + C2H2 -> A3-C14H10 + H { A = 3.02E+03 n = 2.55 E = 13.31 } @@ -2959,7 +3055,6 @@ # Acephenanthrylene # ----------------- - # From A1C2H* P86f: A2R5C2H*-C14H7 + C2H2 -> A3R5--C16H9 { A = 1.34E+04 n = 2.50 E = 5.37 } @@ -2982,7 +3077,6 @@ # Pyrene # ------ - # From A2* P93f: A3*-C14H9 + C2H2 -> A4-C16H10 + H { A = 5.38E+07 n = 1.65 E = 10.71 } @@ -2995,7 +3089,6 @@ # 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 } @@ -3004,7 +3097,6 @@ # 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 } @@ -3103,3 +3195,5 @@ 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]. + +Let M10= 2.5 [H2] + 16.3 [H2O] + 0.88 [AR] + 1.0 [OTHER].