--- CaltechMech.mech 2015/01/26 00:03:15 2.2 +++ CaltechMech.mech 2015/03/25 01:15:43 2.3 @@ -250,15 +250,10 @@ 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 } - -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 } + +G37f: S-CH2 + OH -> CH2O + H { A = 3.00E+13 n = .00 E = .00 } +G38 : S-CH2 + H2O -> CH2O + H2 { A = 6.82E+10 n = .25 E = -3.91 } +G39f: S-CH2 + CO2 -> CH2O + CO { A = 1.40E+13 n = .00 E = .00 } # Formaldehyde @@ -266,30 +261,30 @@ # 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 +G40f: 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 +G41f: 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 } +G42f: CH2O + H -> HCO + H2 { A = 5.86E+03 n = 3.13 E = 6.34 } # Xu, Zhu, Lin 2006 -G44f: CH2O + OH -> HCO + H2O { A = 1.94E+06 n = 2.11 E = -7.06 } +G43f: CH2O + OH -> HCO + H2O { A = 1.94E+06 n = 2.11 E = -7.06 } -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 } +G44f: CH2O + O -> HCO + OH { A = 3.90E+13 n = .00 E = 14.81 } +G45f: CH2O + O2 -> HCO + HO2 { A = 1.00E+14 n = .00 E = 167.36 } +G46f: 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 } +G47f: CH2O + CH -> CH2CO + H { A = 2.68E+14 n = -0.32 E = -3.21 } # Methyl radical @@ -297,123 +292,134 @@ # Golden 2013 # Baulch et al.; Troe Ushakov -G49f: CH3 + H + M9 -> CH4 + M9 { A = 2.79E+34 n = -5.10 E = 11.65 +G48f: 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 -G50f: CH3 + O -> CH2O + H { A = 5.54E+13 n = 0.05 E = -0.57 } - -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 } -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 } +# Harding, Klippenstein, Georgievskii 2005 - Total rate +# Xu, Ragunath, Lin 2015 - Branching ratios +G49f: CH3 + O -> CH2O + H { A = 3.32E+13 n = 0.05 E = -0.57 } +G50f: CH3 + O -> HCO + H2 { A = 2.22E+13 n = 0.05 E = -0.57 } + +# Jasper, Klippenstein, Harding, Ruscic 2007 - fitted 1atm +# rate for S-CH2 80% larger than Xu, Xu, Lin 2007 +G51f: CH3 + OH -> T-CH2 + H2O { A = 4.24E+04 n = 2.57 E = 16.73 } +G52f: CH3 + OH -> S-CH2 + H2O { A = 1.81E+15 n = -0.77 E = 5.54 } # Petersen et al. 2007 -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 +G53f: CH3 + O2 -> CH3O + O { A = 1.38E+13 n = .00 E = 127.70 } +G54f: CH3 + O2 -> CH2O + OH { A = 5.87E+11 n = .00 E = 57.91 } +G55f: 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 } -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 } +G56f: CH3O2 + CH3 -> CH3O + CH3O { A = 1.00E+13 n = .00 E = -5.02 } +G57 : CH3O2 + CH3O2 -> CH3O + CH3O + O2 { A = 1.40E+16 n = -1.61 E = 7.78 } +G58 : CH3O2 + HO2 -> CH3O + OH + O2 { A = 2.47E+11 n = .00 E = -6.57 } +G59 : CH3O2 + CH2O -> CH3O + OH + HCO { A = 1.99E+12 n = .00 E = 48.83 } # Jasper, Klippensteion, Harding 2009 -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 } +G60f: CH3 + HO2 -> CH3O + OH { A = 1.00E+12 n = 0.29 E = -2.87 } +G61f: CH3 + HO2 -> CH4 + O2 { A = 1.19E+05 n = 2.23 E = -12.65 } -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 } +G62f: CH3 + H2O2 -> CH4 + HO2 { A = 2.45E+04 n = 2.47 E = 21.67 } +G63f: CH3 + HCO -> CH4 + CO { A = 2.65E+13 n = .00 E = .00 } +G64f: 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 } +G65f: CH3 + C -> C2H2 + H { A = 5.00E+13 n = .00 E = .00 } +G66f: CH3 + CH -> C2H3 + H { A = 3.00E+13 n = .00 E = .00 } +G67f: CH3 + T-CH2 -> C2H4 + H { A = 1.00E+14 n = .00 E = .00 } +G68f: CH3 + S-CH2 -> C2H4 + H { A = 1.20E+13 n = .00 E = -2.39 } +G69f: CH3 + CH3 -> C2H5 + H { A = 6.84E+12 n = 0.10 E = 44.35 } -# Methoxy radical -# --------------- +# Methoxy/hydroxymethyl radicals +# ------------------------------ # Dames & Golden 2013 -G72f: CH2OH + M9 -> CH2O + H + M9 { A = 3.50E+21 n = -1.99 E = 100.41 +G70f: CH2OH + M11 -> CH2O + H + M11 { 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 +G71f: CH3O + M11 -> CH2O + H + M11 { 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 - 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 } +# Xu, Xu, Lin 2007 +G72f: CH3O + H -> CH3 + OH { A = 4.65E+13 n = 0.28 E = 0.12 } +G73f: CH2OH + H -> CH3 + OH { A = 1.82E+13 n = 0.16 E = 0.47 } +G74f: CH3O + H -> CH2O + H2 { A = 7.59E+08 n = 1.50 E = -2.17 } +G75f: CH2OH + H -> CH2O + H2 { A = 4.01E+06 n = 1.86 E = 0.62 } + +G76f: CH3O + O -> CH2O + OH { A = 1.00E+13 n = .00 E = .00 } +G77f: CH3O + OH -> CH2O + H2O { A = 5.00E+12 n = .00 E = .00 } + +# Chai, Hu, Dibble 2014 +G78f: CH3O + O2 -> CH2O + HO2 { A = 2.29E+03 n = 2.40 E = 1.73 } -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 } +G79f: CH2OH + O -> CH2O + OH { A = 1.00E+13 n = .00 E = .00 } +G80f: CH2OH + OH -> CH2O + H2O { A = 5.00E+12 n = .00 E = .00 } -G89f: CH3O + H -> CH2OH + H { A = 4.15E+07 n = 1.63 E = 8.05 } +# Grotheer et al. 1988 +G81f: CH2OH + O2 -> CH2O + HO2 { A = 2.41E+14 n = .00 E = 20.99 } # 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 } +G82f: CH4 + H -> CH3 + H2 { A = 6.60E+08 n = 1.62 E = 45.36 } +G83f: CH4 + O -> CH3 + OH { A = 1.02E+09 n = 1.50 E = 35.98 } +G84f: CH4 + OH -> CH3 + H2O { A = 1.00E+08 n = 1.60 E = 13.05 } +G85f: CH4 + T-CH2 -> CH3 + CH3 { A = 2.46E+06 n = 2.00 E = 34.60 } +G86f: 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 } +G87f: 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 } +# Jasper, Klippenstein, Harding, Ruscic 2007 - refitted +G90f: CH3OH + M9 -> CH3 + OH + M9 { A = 5.39E+51 n = -9.36 E = 435.03 + Ai= 2.08E+18 ni= -0.61 Ei= 387.21 + fcA = 0.2344 fctA = 59.51 + fcb = 0.7656 fctb = 1910 + fcc = 1.0 fctc = 9374 } +G91f: CH3OH + M9 -> S-CH2 + H2O + M9 { A = 7.76E+48 n = -8.68 E = 420.25 + Ai= 3.12E+18 ni= -1.02 Ei= 383.74 + fcA = 0.0078 fctA = 47310 + fcb = 0.9922 fctb = 943 + fcc = 1.0 fctc = 47110 } + +# Meana-Paneda, Truhlar, Fernandez-Ramos 2011 +G92f: CH3OH + H -> CH2OH + H2 { A = 1.54E+06 n = 2.35 E = 24.73 } +G93f: CH3OH + H -> CH3O + H2 { A = 5.48E+06 n = 2.15 E = 46.44 } + +G94f: CH3OH + O -> CH2OH + OH { A = 3.88E+05 n = 2.50 E = 12.97 } +G95f: CH3OH + O -> CH3O + OH { A = 1.30E+05 n = 2.50 E = 20.92 } + +# Zaczek, Lam, Davidson, Hanson 2014 - Total rate +# Rasmussen, Wassard et al. 2008 - branching ratios +G96f: CH3OH + OH -> CH2OH + H2O { A = 5.14E+04 n = 2.62 E = -2.85 } +G97f: CH3OH + OH -> CH3O + H2O { A = 5.71E+03 n = 2.62 E = -2.85 } + +# Peukert & Michael 2013 +G98f: CH3OH + CH3 -> CH2OH + CH4 { A = 4.90E+12 n = 0.01 E = 63.09 } +G99f: CH3OH + CH3 -> CH3O + CH4 { A = 2.31E+13 n = -0.48 E = 61.07 } + +# Klippenstein, Harding, Davis, Tomlin, Skodje 2011 +G100: CH3OH + O2 -> CH2OH + HO2 { A = 3.58E+05 n = 2.27 E = 178.92 } + +# Alecu & Truhlar 2011 +G101f: CH3OH + HO2 -> CH2OH + H2O2 { A = 1.62E-04 n = 4.99 E = 44.26 } +G102f: CH3OH + HO2 -> CH3O + H2O2 { A = 8.65E-01 n = 3.89 E = 77.04 } # Acetyl radical @@ -616,7 +622,7 @@ G179 : C2H4 + O2 -> CH3 + CO2 + H { A = 4.90E+12 n = 0.42 E = 317.15 } # Miller & Klippenstein 2013 -G180f: C2H4 + CH3 -> C2H3 + CH4 { A = 2.06E-01 n = 3.94 E = 51.98 } +G180f: C2H4 + CH3 -> C2H3 + CH4 { A = 1.05E+02 n = 3.22 E = 59.86 } 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 @@ -635,43 +641,44 @@ fcc = 1.0 fctc = 6882 } G183f: C2H5 + H -> C2H4 + H2 { A = 2.00E+12 n = .00 E = .00 } +G184f: C2H5 + OH -> C2H4 + H2O { A = 2.41E+13 n = .00 E = .00 } # Miller, Klippenstein & Robertson 2000 -G184f: C2H5 + O2 -> C2H4 + HO2 { A = 1.92E+07 n = 1.02 E = -8.51 } +G185f: C2H5 + O2 -> C2H4 + HO2 { A = 1.92E+07 n = 1.02 E = -8.51 } # Zhu, Xu & Lin 2004 -G185f: C2H5 + CH3 -> C2H4 + CH4 { A = 1.18E+04 n = 2.45 E = 12.22 } +G186f: C2H5 + CH3 -> C2H4 + CH4 { A = 1.18E+04 n = 2.45 E = 12.22 } # Harding, Klippenstein & Georgievskii 2005 -G186f: C2H5 + O -> CH3 + CH2O { A = 3.17E+13 n = 0.03 E = -1.65 } +G187f: C2H5 + O -> CH3 + CH2O { A = 3.17E+13 n = 0.03 E = -1.65 } # Ludwig et al. 2006 -G187f: C2H5 + HO2 -> C2H5O + OH { A = 3.10E+13 n = .00 E = .00 } +G188f: C2H5 + HO2 -> C2H5O + OH { A = 3.10E+13 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 } +G189f: C2H5 + HCO -> C2H6 + CO { A = 1.20E+14 n = .00 E = .00 } +G190f: C2H5 + HO2 -> C2H6 + O2 { A = 3.00E+11 n = .00 E = .00 } +G191f: C2H5 + HO2 -> C2H4 + H2O2 { A = 3.00E+11 n = .00 E = .00 } # Ethoxy radical # -------------- # Dames 2014 -G191f: C2H5O + M9 -> CH3 + CH2O + M9 { A = 4.70E+25 n = -3.00 E = 69.17 +G192f: 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 -G192f: C2H5O + O2 -> CH3CHO + HO2 { A = 2.29E+10 n = .00 E = 3.66 } +G193f: C2H5O + O2 -> CH3CHO + HO2 { A = 2.29E+10 n = .00 E = 3.66 } # Ethane # ------ # Oehlschlaeger et al. 2005 -G193f: C2H6 + M9 -> 2 CH3 + M9 { A = 3.72E+65 n =-13.14 E = 425.01 +G194f: 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 @@ -679,21 +686,21 @@ # Chakraborty, Zhao, Lin, & Truhlar 2006 # Fit 500-2000K -G194f: C2H6 + H -> C2H5 + H2 { A = 1.70E+05 n = 2.70 E = 24.02 } +G195f: C2H6 + H -> C2H5 + H2 { A = 1.70E+05 n = 2.70 E = 24.02 } # Huynh, Zhang, Truong 2008 -G195f: C2H6 + O -> C2H5 + OH { A = 3.17E+01 n = 3.80 E = 13.10 } +G196f: C2H6 + O -> C2H5 + OH { A = 3.17E+01 n = 3.80 E = 13.10 } # Krasnoperov & Michael 2004 -G196f: C2H6 + OH -> C2H5 + H2O { A = 1.61E+06 n = 2.22 E = 3.10 } +G197f: C2H6 + OH -> C2H5 + H2O { A = 1.61E+06 n = 2.22 E = 3.10 } # Carstensen & Dean 2005 -G197f: C2H6 + HO2 -> C2H5 + H2O2 { A = 2.61E+02 n = 3.37 E = 66.58 } +G198f: C2H6 + HO2 -> C2H5 + H2O2 { A = 2.61E+02 n = 3.37 E = 66.58 } -G198f: C2H6 + S-CH2 -> C2H5 + CH3 { A = 4.00E+13 n = .00 E = -2.30 } +G199f: C2H6 + S-CH2 -> C2H5 + CH3 { A = 4.00E+13 n = .00 E = -2.30 } # Peukert, Labbe, Sivaramakrishnan, Michael 2013 -G199f: C2H6 + CH3 -> C2H5 + CH4 { A = 3.45E+01 n = 3.44 E = 43.47 } +G200f: C2H6 + CH3 -> C2H5 + CH4 { A = 3.45E+01 n = 3.44 E = 43.47 } # Propyl radicals @@ -701,71 +708,71 @@ # Curran 2006 - HPL -G200f: C3H6 + H + M9 -> N-C3H7 + M9 { A = 6.26E+38 n = -6.66 E = 29.29 +G201f: 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 } -G201f: C3H6 + H + M9 -> I-C3H7 + M9 { A = 8.70E+42 n = -7.50 E = 19.75 +G202f: 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 } -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 } +G203f: N-C3H7 + H -> C2H5 + CH3 { A = 3.70E+24 n = -2.92 E = 52.32 } +G204f: I-C3H7 + H -> C2H5 + CH3 { A = 1.40E+28 n = -3.94 E = 66.59 } +G205f: N-C3H7 + H -> C3H6 + H2 { A = 1.80E+12 n = .00 E = .00 } +G206f: I-C3H7 + H -> C3H6 + H2 { A = 3.20E+12 n = .00 E = .00 } +G207f: N-C3H7 + O -> C2H5 + CH2O { A = 9.60E+13 n = .00 E = .00 } +G208f: I-C3H7 + O -> CH3CHO + CH3 { A = 9.60E+13 n = .00 E = .00 } +G209f: N-C3H7 + OH -> C3H6 + H2O { A = 2.41E+13 n = .00 E = .00 } +G210f: I-C3H7 + OH -> C3H6 + H2O { A = 2.41E+13 n = .00 E = .00 } # DeSain, Miller, Klippenstein & Taatjes 2003 -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 } +G211f: N-C3H7 + O2 -> C3H6 + HO2 { A = 3.70E+16 n = -1.63 E = 14.30 } +G212f: 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 -G212f: N-C3H7 + CH3 -> C3H6 + CH4 { A = 3.31E+12 n = .00 E = -3.22 } +G213f: N-C3H7 + CH3 -> C3H6 + CH4 { A = 3.31E+12 n = .00 E = -3.22 } # Propane # ------- # From Tsang 1988 -G213f: N-C3H7 + H + M9 -> C3H8 + M9 { A = 4.42E+61 n =-13.55 E = 47.52 +G214f: 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 } -G214f: I-C3H7 + H + M9 -> C3H8 + M9 { A = 1.70E+58 n =-12.08 E = 47.13 +G215f: 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 -G215f: C3H8 + M9 -> C2H5 + CH3 + M9 { A = 5.64E+74 n =-15.74 E = 413.04 +G216f: 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 -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 } +G217f: C3H8 + H -> N-C3H7 + H2 { A = 9.36E+07 n = 1.97 E = 34.31 } +G218f: C3H8 + H -> I-C3H7 + H2 { A = 7.60E+07 n = 1.86 E = 23.43 } -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 } +G219f: C3H8 + O -> N-C3H7 + OH { A = 1.90E+05 n = 2.68 E = 15.55 } +G220f: C3H8 + O -> I-C3H7 + OH { A = 4.76E+04 n = 2.71 E = 8.81 } # Sivaramkrishnan, Srinivasan, Su, Michael 2009 -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 } +G221f: C3H8 + OH -> N-C3H7 + H2O { A = 5.15E+03 n = 2.94 E = -1.75 } +G222f: C3H8 + OH -> I-C3H7 + H2O { A = 1.81E+05 n = 2.44 E = -2.24 } -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 } +G223f: C3H8 + CH3 -> N-C3H7 + CH4 { A = 9.03E-01 n = 3.65 E = 29.93 } +G224f: C3H8 + CH3 -> I-C3H7 + CH4 { A = 1.51E+00 n = 3.46 E = 29.93 } +G225f: C3H8 + HO2 -> N-C3H7 + H2O2 { A = 4.76E+04 n = 2.55 E = 69.00 } +G226f: C3H8 + HO2 -> I-C3H7 + H2O2 { A = 9.63E+03 n = 2.60 E = 58.20 } @@ -864,67 +871,69 @@ R038f: C3H3 + T-CH2 -> C4H4 + H { A = 5.00E+13 n = .00 E = .00 } -# Propyne & Allene -# ---------------- +# 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 } +R039f: C2H4 + CH -> A-C3H4 + H { A = 9.98E+14 n = -0.31 E = .00 } # 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 } +R041f: A-C3H4 + H -> C2H2 + CH3 { A = 8.95E+13 n = -0.02 E = 47.07 } +R042f: A-C3H4 + H -> A-C3H5 { A = 2.01E+49 n =-10.77 E = 82.10 } +R043f: A-C3H4 + H -> T-C3H5 { A = 6.70E+42 n =-12.46 E = 68.45 } -# 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 } +# Giri, Fernandes, Bentz, Hippler, Olzmann 2011 +R040f: A-C3H4 + M0 -> C3H3 + H + M0 { A = 2.15E+43 n = -6.81 E = 420.61 } # 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 = 2.06E-01 n = 3.94 E = 51.98 } -R057f: A-C3H4 + HO2 -> C3H3 + H2O2 { A = 9.76E+10 n = 0.12 E = 97.78 } +R044f: A-C3H4 + H -> C3H3 + H2 { A = 1.33E+06 n = 2.53 E = 51.21 } +R045f: A-C3H4 + OH -> C3H3 + H2O { A = 1.31E-01 n = 4.20 E = -3.60 } +R046f: A-C3H4 + CH3 -> C3H3 + CH4 { A = 1.05E+02 n = 3.22 E = 59.86 } +R047f: A-C3H4 + HO2 -> C3H3 + H2O2 { A = 9.76E+10 n = 0.12 E = 97.78 } # 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 } +R048f: A-C3H4 + O -> C2H4 + CO { A = 9.63E+06 n = 2.05 E = 0.75 } + +# Liu, Maluc, Jonah 1988 +R049f: A-C3H4 + OH -> CH2CO + CH3 { A = 4.03E+12 n = .00 E = -0.83 } + + +# Propyne +# ------- + +# Miller & Klippenstein 2003 (1bar) +R050f: A-C3H4 -> P-C3H4 { A = 7.76E+39 n = -7.80 E = 328.22 } + +# Sheen, Rosado-Reyes, Tsang 2013 +R051f: C2H2 + CH3 -> P-C3H4 + H { A = 1.48E+11 n = 0.60 E = 59.86 } +R052f: P-C3H4 + H -> A-C3H4 + H { A = 1.58E+18 n = -1.00 E = 50.72 } + +# Miller, Senosiain, Klippenstein, Georgievskii 2008 - P=1bar +R053f: P-C3H4 + H -> T-C3H5 { A = 8.83E+52 n =-12.36 E = 68.81 } +R054f: P-C3H4 + H -> S-C3H5 { A = 1.53E+49 n =-11.97 E = 59.18 } + +# Giri, Fernandes, Bentz, Hippler, Olzmann 2011 +R055f: P-C3H4 + M0 -> C3H3 + H + M0 { A = 2.15E+43 n = -6.81 E = 420.61 } + +# 1/2 the rate for C2H6 +R056f: P-C3H4 + H -> C3H3 + H2 { A = 8.50E+04 n = 2.70 E = 24.02 } +R057f: P-C3H4 + O -> C3H3 + OH { A = 1.59E+01 n = 3.80 E = 13.10 } +R058f: P-C3H4 + OH -> C3H3 + H2O { A = 8.05E+05 n = 2.22 E = 3.10 } +R059f: P-C3H4 + CH3 -> C3H3 + CH4 { A = 1.73E+01 n = 3.44 E = 43.47 } +R060f: P-C3H4 + HO2 -> C3H3 + H2O2 { A = 1.30E+02 n = 3.37 E = 66.58 } # 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 } +R061f: P-C3H4 + O -> C2H4 + CO { A = 1.85E+09 n = 1.28 E = 10.34 } +R062f: 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 } -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 } +R063f: P-C3H4 + OH -> CH2CO + CH3 { A = 2.10E+01 n = 3.22 E = -1.76 } +R064f: P-C3H4 + OH -> C2H5 + CO { A = 1.28E+09 n = 0.73 E = 10.79 } # Propenal @@ -940,107 +949,120 @@ R070 : C2H3CHO + CH3 -> C2H3 + CO + CH4 { A = 1.55E+00 n = 3.70 E = 10.10 } -# 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 } +# Allyl radical +# ------------- -# 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 } +# Stoliarov et al. 2002 - 1.33bar +R071f: C2H3 + CH3 -> A-C3H5 + H { A = 1.93E+18 n = -1.25 E = 32.09 } # 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 } +R072f: 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 } +R073f: A-C3H5 + OH -> A-C3H4 + H2O { A = 6.03E+12 n = .00 E = .00 } +R074f: A-C3H5 + CH3 -> A-C3H4 + CH4 { A = 3.01E+12 n = -0.32 E = -0.55 } +R075f: A-C3H5 + C2H3 -> A-C3H4 + C2H4 { A = 2.41E+12 n = .00 E = .00 } +R076f: A-C3H5 + C2H5 -> A-C3H4 + C2H6 { A = 9.64E+11 n = .00 E = -0.55 } + +# Lynch, Annesley, Aul, Yang, Tranter 2013 +R077f: A-C3H5 + A-C3H5 -> A-C3H4 + C3H6 { A = 7.50E+11 n = .00 E = .00 } + +# Hoyermann, et al. 2009 - equipartition +# Rate revised based on updated C2H5+O +R078f: A-C3H5 + O -> C2H3CHO + H { A = 1.69E+13 n = 0.03 E = -1.65 } +R079 : A-C3H5 + O -> C2H4 + CO + H { A = 1.69E+13 n = 0.03 E = -1.65 } # 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 } +R080f: A-C3H5 + O2 -> A-C3H4 + HO2 { A = 2.06E+04 n = 2.19 E = 73.60 } +R081f: A-C3H5 + O2 -> C2H3CHO + OH { A = 3.36E+05 n = 1.81 E = 80.29 } +R082 : A-C3H5 + O2 -> C2H2 + CH2O + OH { A = 9.71E+20 n = -2.70 E = 104.52 } +R083f: A-C3H5 + O2 -> CH2CHO + CH2O { A = 3.08E+09 n = 0.37 E = 70.75 } + # From A1CH2+HO2 -R089f: A-C3H5 + HO2 -> C3H5O + OH { A = 1.19E+09 n = 1.03 E = -9.41 } +R084f: A-C3H5 + HO2 -> C3H5O + OH { A = 1.19E+09 n = 1.03 E = -9.41 } + + +# Propen-2-yl radical +# ------------------- + +# From C2H3 +R085f: T-C3H5 + H -> P-C3H4 + H2 { A = 3.00E+13 n = .00 E = .00 } +R086f: T-C3H5 + OH -> P-C3H4 + H2O { A = 5.00E+12 n = .00 E = .00 } +R087f: T-C3H5 + O2 -> P-C3H4 + HO2 { A = 1.34E+06 n = 1.61 E = -1.61 } +R088f: T-C3H5 + CH3 -> P-C3H4 + CH4 { A = 9.03E+12 n = .00 E = -3.20 } + +# From C2H5 +R089f: T-C3H5 + H -> A-C3H4 + H2 { A = 2.00E+12 n = .00 E = .00 } +R090f: T-C3H5 + OH -> A-C3H4 + H2O { A = 2.41E+13 n = .00 E = .00 } +R091f: T-C3H5 + O2 -> A-C3H4 + HO2 { A = 1.92E+07 n = 1.02 E = -8.51 } +R092f: T-C3H5 + CH3 -> A-C3H4 + CH4 { A = 1.18E+04 n = 2.45 E = 12.22 } + +R093f: T-C3H5 + O -> CH2CO + CH3 { A = 6.00E+13 n = .00 E = .00 } +R094 : T-C3H5 + HO2 -> CH2CO + CH3 + OH { A = 2.00E+13 n = .00 E = .00 } + +# Adapted from C2H3+O2 (both reactions lumped) +R095 : T-C3H5 + O2 -> CH2O + CH3 + CO { A = 8.72E+16 n = -1.49 E = 3.66 } + + +# Propen-1-yl radical +# ------------------- +# From C2H3 + +# Miller, Senosiain, Klippenstein, Georgievskii 2008 +# Refitted 800K-2500K - P=1bar +R096f: C2H2 + CH3 -> S-C3H5 { A = 7.45E+43 n =-10.13 E = 77.50 } + +R097f: S-C3H5 + H -> P-C3H4 + H2 { A = 1.50E+13 n = .00 E = .00 } +R098f: S-C3H5 + OH -> P-C3H4 + H2O { A = 2.50E+12 n = .00 E = .00 } +R099f: S-C3H5 + O2 -> P-C3H4 + HO2 { A = 6.70E+05 n = 1.61 E = -1.61 } +R100f: S-C3H5 + CH3 -> P-C3H4 + CH4 { A = 4.52E+12 n = .00 E = -3.20 } -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 } +R101f: S-C3H5 + O -> C2H5 + CO { A = 6.00E+13 n = .00 E = .00 } +R102 : S-C3H5 + HO2 -> C2H5 + CO + OH { A = 2.00E+13 n = .00 E = .00 } + +R103f: S-C3H5 + O2 -> CH3CHO + HCO { A = 4.05E+17 n = -1.86 E = 4.88 } +R104f: S-C3H5 + O2 -> CH3CHO + CO + H { A = 2.22E+16 n = -1.35 E = 3.28 } # 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 } +R105f: C3H5O -> C2H3CHO + H { A = 1.00E+14 n = .00 E = 121.75 } +R106f: C3H5O -> C2H3 + CH2O { A = 2.03E+12 n = 0.09 E = 98.58 } +R107f: 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 } +# High pressure limit (backward rate) +# -> Harding, Klippenstein, & Georgievskii 2007 +# Fall-off +# -> Hung, Tsai, Matsui, Wang, Miyoshi 2015 (1atm) +# -> Stoliarov et al. 2002 (20% higher) +R108f: C3H6 -> A-C3H5 + H { A = 3.87E+57 n =-12.22 E = 476.14 } +R109f: C3H6 -> C2H3 + CH3 { A = 9.20E+70 n =-15.96 E = 537.86 } +R110f: C3H6 -> H2C2 + CH4 { A = 4.61E+68 n =-15.76 E = 522.21 } # 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 } +R114f: C3H6 + H -> C2H4 + CH3 { A = 2.67E+12 n = 0.47 E = 22.73 } +R115f: C3H6 + H -> A-C3H5 + H2 { A = 6.03E+05 n = 2.39 E = 18.79 } +R116f: C3H6 + H -> S-C3H5 + H2 { A = 8.58E+02 n = 3.25 E = 50.90 } +R117f: 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 } +# Badra, Khaled, Raj Giri, Farooq 2015 +R118f: C3H6 + OH -> A-C3H5 + H2O { A = 4.19E+13 n = .00 E = 19.46 } +R119f: C3H6 + OH -> S-C3H5 + H2O { A = 1.67E+13 n = .00 E = 18.87 } +R120f: C3H6 + OH -> T-C3H5 + H2O { A = 4.33E+12 n = .00 E = 18.97 } # 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 } +R121f: C3H6 + O -> CH2CHO + CH3 { A = 8.12E+08 n = 1.25 E = 2.26 } +R122f: 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) @@ -1048,38 +1070,8 @@ 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 = 1.03E-01 n = 3.94 E = 51.98 } -R127f: C3H6 + CH3 -> T-C3H5 + CH4 { A = 5.15E-02 n = 3.94 E = 51.98 } - - -# Hexadiyene -# ---------- - -# 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 } +R126f: C3H6 + CH3 -> S-C3H5 + CH4 { A = 5.25E+01 n = 3.22 E = 59.86 } +R127f: C3H6 + CH3 -> T-C3H5 + CH4 { A = 2.63E+01 n = 3.22 E = 47.31 } @@ -1173,8 +1165,8 @@ 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 } +H38f: C4H4 + CH3 -> N-C4H3 + CH4 { A = 5.25E+01 n = 3.22 E = 59.86 } +H39f: C4H4 + CH3 -> I-C4H3 + CH4 { A = 2.63E+01 n = 3.22 E = 47.31 } # From C2H4 H40f: C4H4 + O -> C3H3 + HCO { A = 6.00E+08 n = 1.45 E = -3.60 } @@ -1240,7 +1232,7 @@ 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 } +B14f: C4H6 + CH3 -> N-C4H5 + CH4 { A = 1.05E+02 n = 3.22 E = 59.86 } B15f: C4H6 + HO2 -> N-C4H5 + H2O2 { A = 1.66E+10 n = 0.36 E = 95.13 } # Adapted from C2H4 - 3kcal @@ -1248,7 +1240,7 @@ 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 } +B20f: C4H6 + CH3 -> I-C4H5 + CH4 { A = 5.25E+01 n = 3.22 E = 47.31 } B21f: C4H6 + HO2 -> I-C4H5 + H2O2 { A = 8.31E+09 n = 0.36 E = 82.58 } # From C3H6 + O (x2) @@ -1278,19 +1270,19 @@ # 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 +# Revised based on C3H6+X->A-C3H5 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 } +B32f: D-C4H6 + H -> I-C4H5 + H2 { A = 6.03E+05 n = 2.39 E = 18.79 } +B33f: D-C4H6 + O -> I-C4H5 + OH { A = 1.43E+02 n = 3.37 E = 0.73 } +B34f: D-C4H6 + OH -> I-C4H5 + H2O { A = 4.19E+13 n = .00 E = 19.46 } 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 } +B36f: D-C4H6 + CH3 -> I-C4H5 + CH4 { A = 4.57E-01 n = 3.65 E = 29.93 } -# 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 } +# From C3H6+X->T-C3H5 +#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 = 1.49E+02 n = 3.38 E = 37.28 } +B39f: D-C4H6 + OH -> S-C4H5 + H2O { A = 4.33E+12 n = .00 E = 18.97 } +B40f: D-C4H6 + CH3 -> S-C4H5 + CH4 { A = 2.63E+01 n = 3.22 E = 47.31 } # From A-C3H4 + O B41f: D-C4H6 + O -> C3H6 + CO { A = 9.63E+06 n = 2.05 E = 0.75 } @@ -1449,7 +1441,7 @@ # Reactions of OQ'OOH # all products lumped -HX29: OC6H11OOH -> C5H10 + CH2CO + OH { A = 3.26E+09 n = 1.93 E = 161.11 } +HX29 : OC6H11OOH -> C2H5 + CH3CHO + CH2CO + OH { A = 3.26E+09 n = 1.93 E = 161.11 } # Reactions of QO # all products lumped @@ -2195,9 +2187,9 @@ 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 } +BN18f: A1OH-C6H6O + H -> A1O-C6H5O + H2 { A = 5.48E+06 n = 2.15 E = 46.44 } +BN19f: A1OH-C6H6O + OH -> A1O-C6H5O + H2O { A = 5.71E+03 n = 2.62 E = -2.85 } +BN20f: A1OH-C6H6O + CH3 -> A1O-C6H5O + CH4 { A = 2.31E+13 n = -0.48 E = 61.07 } # Brezinsky et al. 1998 #N21f: A1OH-C6H6O + O2 -> A1O-C6H5O + HO2 { A = 7.32E+13 n = .00 E = 173.22 } @@ -2322,15 +2314,13 @@ # 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 } +T23f: A1CH2O-C7H7O -> A1CHO-C7H6O + H { A = 5.26E+28 n = -5.08 E = 93.09 } +T24f: A1CH2O-C7H7O -> A1--C6H5 + CH2O { A = 7.21E+33 n = -6.21 E = 154.18 } +T25f: A1CH2O-C7H7O -> A1-C6H6 + HCO { A = 2.37E+32 n = -6.10 E = 120.54 } + +# Choi, Xia, Park, Lin 2000 - written as reverse +T26f: A1CHO-C7H6O + H -> A1--C6H5 + CH2O { A = 7.38E+13 n = -0.10 E = 50.49 } # From CH3O (x2/3) T27f: A1CH2O-C7H7O + H -> A1CHO-C7H6O + H2 { A = 1.33E+13 n = .00 E = .00 } @@ -2359,10 +2349,10 @@ # 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 } +T37f: HOA1CH3-C7H8O + H -> OA1CH3-C7H7O + H2 { A = 5.48E+06 n = 2.15 E = 46.44 } 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 } +T39f: HOA1CH3-C7H8O + OH -> OA1CH3-C7H7O + H2O { A = 5.71E+03 n = 2.62 E = -2.85 } +T40f: HOA1CH3-C7H8O + CH3-> OA1CH3-C7H7O + CH4 { A = 2.31E+13 n = -0.48 E = 61.07 } T41 : OA1CH3-C7H7O -> C5H4CH2 + CO + H { A = 2.90E+10 n = .00 E = 152.40 } @@ -2815,7 +2805,7 @@ # Methoxy-Naphthyl # ---------------- -MN20f: A2CH2O-C11H9O -> A2CHO-C11H8O + H { A = 1.27E+13 n = .00 E = 86.19 } +MN20f: A2CH2O-C11H9O -> A2CHO-C11H8O + H { A = 5.26E+28 n = -5.08 E = 93.09 } 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 } @@ -3197,3 +3187,6 @@ 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]. + +Let M11= 2.0 [H2] + 6.0 [H2O] + 0.85 [AR] + 1.50 [CO] + 2.00 [CO2] + 2 [CH4] + 1.0 [OTHER]. +