!************************************************************** ! ! A DETAILED KINETIC MODEL OF C2- AND C3- FUEL COMBUSTION ! ! Interim version, June 1999 ! ! ! Hai Wang & Alenxander Laskin, University of Delaware ! ! and ! ! C.K. Law, Princeton University ! ! ! !!! Please do not distribute !!! ! ! Technical contact: ! ! Hai Wang ! Department of Mechanical Engineering Phone: (302) 831-4464 ! University of Delaware FAX: (302) 831-3619 ! Newark, DE 19716 E-mail: hwang@me.udel.edu ! !************************************************************** ! ! Document/publications: ! ! (1) Wang, H and Laskin, A., A Comprehensive Kinetic Model ! of Ethylene and Acetylene Oxidation at High Temperatures, ! Progress report, Princeton/AFOSR, December1998. ! ! (2) "On initiation reactions of acetylene oxidation in ! shock tubes. A quantum mechanical and detailed kinetic ! modeling study," Laskin, A., Wang, H., Chemical Physics ! Letters 303, pp. 43-49 (1999). ! ! (3) "Propene pyrolysis and oxidation kinetics in a flow reactor ! and laminar premixed flames," Davis, S. G., Law, C. K., ! Wang, H., Combustion and Flame, in press, 1999. ! ! (4) "Propyne pyrolysis in a flow reactor: an experimental, RRKM, ! and detailed kinetic modeling study," Davis, S. G., ! Law, C. K., Wang, H., Journal of Physical Chemistry, in press, ! 1999. ! ! (5) "An experimental and kinetic modeling study of propyne ! oxidation." Davis, S. G., Law, C. K., Wang, H., Twenty- ! Seventh Symposium (International) on Combustion, The Combustion ! Institute, Pittsburgh, 1999, pp. 305-312. ! ! (6) "A detailed kinetic modeling study of aromatics formation, ! growth and oxidation in laminar premixed ethylene and acetylene ! flames," Wang, H., Frenklach, M., Combustion and Flame 110, ! pp. 173-221 (1997). ! ! (7) "On the structure of non-sooting counterflow ethylene and ! acetylene diffusion flames," Sun, C. J., Sung, C. J., Wang, H., ! Law, C. K., Combustion and Flame 107, pp.321-335 (1996). ! ! (8) "Detailed oxidation kinetics and flame inhibition effects ! of chloromethane," Wang, H., Hahn, T. O., Sung, C. J., ! Law, C. K., Combustion and Flame 105, pp.291-307 (1996). ! ! (9) Frenklach, M., Wang, H., Goldenberg, M., Smith, G. P., ! Golden, D. M., Bowman, C. T., Hanson, R. K., Gardiner, W. C., ! and Lissianski, V., GRI-MechÜAn Optimized Detailed Chemical ! Reaction Mechanism for Methane Combustion, GRI Technical ! Report No. GRI-95/0058, November 1, 1995. ! !************************************************************** ELEMENTS O H C N AR END SPECIES H2 H O O2 OH H2O HO2 H2O2 C CH CH2 CH2* CH3 CH4 CO CO2 HCO CH2O CH2OH CH3O CH3OH C2H C2H2 H2CC C2H3 C2H4 C2H5 C2H6 HCCO CH2CO HCCOH C2O CH2CHO CH3CHO CH3CO C3H2 C3H3 pC3H4 aC3H4 cC3H4 aC3H5 CH3CCH2 CH3CHCH C3H6 C2H3CHO nC3H7 iC3H7 C3H8 C4H C4H2 H2C4O n-C4H3 i-C4H3 C4H4 n-C4H5 i-C4H5 C4H6 C4H612 C4H7 C4H81 C6H2 C6H3 l-C6H4 c-C6H4 A1 A1- C6H5O C6H5OH C5H6 C5H5 C5H4O C5H4OH C5H5O AR N2 END REACTIONS ! Reactions of H2/O2 H + O2 = O + OH 8.300E+13 0.000 14413.00 ! GRI1.2 O + H2 = H + OH 5.000E+04 2.670 6290.00 ! GRI1.2 OH + H2 = H + H2O 2.160E+08 1.510 3430.00 ! GRI1.2 OH + OH = O + H2O 3.570E+04 2.400 -2110.00 ! GRI1.2 H + H + M = H2 + M 1.000E+18 -1.000 0.00 ! GRI1.2 H2/0.0/ H2O/0.0/ CH4/2.0/ CO2/0.0/ C2H6/3.00/ AR/0.63/ C2H2/3.00/ C2H4/3.00/ H + H + H2 = H2 + H2 9.000E+16 -0.600 0.00 ! GRI1.2 H + H + H2O = H2 + H2O 6.000E+19 -1.250 0.00 ! GRI1.2 H + H + CO2 = H2 + CO2 5.500E+20 -2.000 0.00 ! GRI1.2 H + OH + M = H2O + M 2.200E+22 -2.000 0.00 ! GRI1.2 H2/0.73/ H2O/3.65/ CH4/2.0/ C2H6/3.0/ AR/0.38/ C2H2/3.00/ C2H4/3.00/ O + H + M = OH + M 5.000E+17 -1.000 0.00 ! GRI1.2 H2/2.0/ H2O/6.0/ CH4/2.0/ CO/1.5/ CO2/2.0/ C2H6/3.0/ AR/0.7/ C2H2/3.00/ C2H4/3.00/ O + O + M = O2 + M 1.200E+17 -1.000 0.00 ! GRI1.2 H2/ 2.4/ H2O/15.4/ CH4/ 2.0/ CO/ 1.75/ CO2/ 3.6/ C2H6/ 3.0/ AR/ 0.83/ C2H2/3.00/ C2H4/3.00/ H + O2 + M = HO2 + M 2.800E+18 -0.860 0.00 ! GRI1.2 O2/0.0/ H2O/0.0/ CO/0.75/ CO2/1.5/ C2H6/1.5/ N2/0.0/ AR/0.0/ C2H2/3.00/ C2H4/3.00/ H + O2 + O2 = HO2 + O2 3.000E+20 -1.720 0.00 ! GRI1.2 !H + O2 + H2O = HO2 + H2O 9.380E+18 -0.760 0.00 ! GRI1.2 H + O2 + H2O = HO2 + H2O 1.652E+19 -0.760 0.00 ! GRI-Mech 1.2a !H + O2 + N2 = HO2 + N2 3.750E+20 -1.720 0.00 ! GRI1.2 H + O2 + N2 = HO2 + N2 2.600E+19 -1.240 0.00 ! New Stanf. measur. H + O2 + AR = HO2 + AR 7.000E+17 -0.800 0.00 ! GRI1.2 OH + OH(+M) = H2O2(+M) 7.400E+13 -0.370 0.00 ! GRI1.2 LOW / 2.300E+18 -0.900 -1700.00/ TROE / 0.7346 94.00 1756.00 5182.00 / H2/2.0/ H2O/6.0/ CH4/2.0/ CO/1.5/ CO2/2.0/ C2H6/3.0/ AR/0.7/ C2H2/3.00/ C2H4/3.00/ ! Reactions of HO2 HO2 + H = O + H2O 3.970E+12 0.000 671.00 ! GRI1.2 !HO2 + H = O2 + H2 2.800E+13 0.000 1068.00 ! GRI1.2 !HO2 + H = OH + OH 1.340E+14 0.000 635.00 ! GRI1.2 HO2 + H = O2 + H2 1.660E+13 0.000 820.00 ! Mueller et al. HO2 + H = OH + OH 7.080E+13 0.000 300.00 ! Mueller et al. ! HO2 + O = OH + O2 2.000E+13 0.000 0.00 ! GRI1.2 !HO2 + OH = O2 + H2O 2.900E+13 0.000 -500.00 ! GRI1.2 HO2 + OH = O2 + H2O 4.640E+13 0.000 -500.00 ! GRI-Mech 1.2a HO2 + HO2 = O2 + H2O2 1.300E+11 0.000 -1630.00 ! GRI1.2 DUPLICATE HO2 + HO2 = O2 + H2O2 4.200E+14 0.000 12000.00 ! GRI1.2 DUPLICATE ! Reactions of H2O2 H2O2 + H = HO2 + H2 1.210E+07 2.000 5200.00 ! GRI1.2 H2O2 + H = OH + H2O 1.000E+13 0.000 3600.00 ! GRI1.2 H2O2 + O = OH + HO2 9.630E+06 2.000 4000.00 ! GRI1.2 H2O2 + OH = HO2 + H2O 1.750E+12 0.000 320.00 ! GRI1.2 DUPLICATE H2O2 + OH = HO2 + H2O 5.800E+14 0.000 9560.00 ! GRI1.2 DUPLICATE ! Reactions of CO/CO2 CO + O + M = CO2 + M 6.020E+14 0.000 3000.00 ! GRI1.2 H2/2.0/ O2/6.0/ H2O/6.0/ CH4/2.0/ CO/1.5/ CO2/3.5/ C2H6/3.0/ AR/0.5/ C2H2/3.00/ C2H4/3.00/ CO + OH = CO2 + H 4.760E+07 1.228 70.00 ! GRI1.2 CO + H2(+M) = CH2O(+M) 4.300E+07 1.500 79600.00 ! GRI1.2 LOW / 5.070E+27 -3.420 84350.00/ TROE / 0.9320 197.00 1540.00 10300.00 / H2/2.0/ H2O/6.0/ CH4/2.0/ CO/1.5/ CO2/2.0/ C2H6/3.0/ AR/0.7/ C2H2/3.00/ C2H4/3.00/ CO + O2 = CO2 + O 2.500E+12 0.000 47800.00 ! GRI1.2 CO + HO2 = CO2 + OH 1.500E+14 0.000 23600.00 ! GRI1.2 ! Reactions of C C + OH = CO + H 5.000E+13 0.000 0.00 ! GRI1.2 C + O2 = CO + O 5.800E+13 0.000 576.00 ! GRI1.2 ! Reactions of CH CH + H = C + H2 1.100E+14 0.000 0.00 ! GRI1.2 CH + O = CO + H 5.700E+13 0.000 0.00 ! GRI1.2 CH + OH = HCO + H 3.000E+13 0.000 0.00 ! GRI1.2 CH + H2 = CH2 + H 1.107E+08 1.790 1670.00 ! GRI1.2 CH + H2O = CH2O + H 5.710E+12 0.000 -755.00 ! GRI1.2 CH + O2 = HCO + O 3.300E+13 0.000 0.00 ! GRI1.2 CH + CO(+M) = HCCO(+M) 5.000E+13 0.000 0.00 ! GRI1.2 LOW / 2.690E+28 -3.740 1936.00/ TROE / 0.5757 237.00 1652.00 5069.00 / H2/2.0/ H2O/6.0/ CH4/2.0/ CO/1.5/ CO2/2.0/ C2H6/3.0/ AR/0.7/ C2H2/3.00/ C2H4/3.00/ CH + CO2 = HCO + CO 3.400E+12 0.000 690.00 ! GRI1.2 ! Reactions of HCO HCO + H(+M) = CH2O(+M) 1.090E+12 0.480 -260.00 ! GRI1.2 LOW / 1.350E+24 -2.570 1425.00/ TROE / 0.7824 271.00 2755.00 6570.00 / H2/2.0/ H2O/6.0/ CH4/2.0/ CO/1.5/ CO2/2.0/ C2H6/3.0/ AR/0.7/ C2H2/3.00/ C2H4/3.00/ HCO + H = CO + H2 7.340E+13 0.000 0.00 ! GRI1.2 HCO + O = CO + OH 3.000E+13 0.000 0.00 ! GRI1.2 HCO + O = CO2 + H 3.000E+13 0.000 0.00 ! GRI1.2 HCO + OH = CO + H2O 5.000E+13 0.000 0.00 ! GRI1.2 HCO + M = CO + H + M 1.870E+17 -1.000 17000.00 ! GRI1.2 beta(H2O)=18 H2/2.0/ H2O/6.0/ CH4/2.0/ CO/1.5/ CO2/2.0/ C2H6/3.0/ C2H2/3.00/ C2H4/3.00/ HCO + O2 = CO + HO2 7.600E+12 0.000 400.00 ! GRI1.2 ! Reactions of CH2(triplet) CH2 + H(+M) = CH3(+M) 2.500E+16 -0.800 0.00 ! GRI1.2 LOW / 3.200E+27 -3.140 1230.00/ TROE / 0.6800 78.00 1995.00 5590.00 / H2/2.0/ H2O/6.0/ CH4/2.0/ CO/1.5/ CO2/2.0/ C2H6/3.0/ AR/0.7/ C2H2/3.00/ C2H4/3.00/ CH2 + H2 = H + CH3 5.000E+05 2.000 7230.00 ! GRI1.2 CH2 + O = HCO + H 8.000E+13 0.000 0.00 ! GRI1.2 CH2 + O2 = HCO + OH 1.056E+13 0.000 1500.00 ! GRI1.2 alpha = 0.8 CH2 + O2 = CO2 + H + H 2.640E+12 0.000 1500.00 ! Wagner's CO/CO2 ratio, alpha = 0.2 CH2 + OH = CH2O + H 2.000E+13 0.000 0.00 ! GRI1.2 CH2 + OH = CH + H2O 1.130E+07 2.000 3000.00 ! GRI1.2 CH2 + HO2 = CH2O + OH 2.000E+13 0.000 0.00 ! GRI1.2 CH2 + C = C2H + H 5.000E+13 0.000 0.00 ! GRI1.2 CH2 + CO(+M) = CH2CO(+M) 8.100E+11 0.500 4510.00 ! GRI1.2 LOW / 2.690E+33 -5.110 7095.00/ TROE / 0.5907 275.00 1226.00 5185.00 / H2/2.0/ H2O/6.0/ CH4/2.0/ CO/1.5/ CO2/2.0/ C2H6/3.0/ AR/0.7/ C2H2/3.00/ C2H4/3.00/ CH2 + CH = C2H2 + H 4.000E+13 0.000 0.00 ! GRI1.2 CH2 + CH2 = C2H2 + H2 3.200E+13 0.000 0.00 ! GRI1.2 ! Reactions of CH2*(singlet) CH2* + N2 = CH2 + N2 1.500E+13 0.000 600.00 ! GRI1.2 CH2* + AR = CH2 + AR 9.000E+12 0.000 600.00 ! GRI1.2 CH2* + H = CH + H2 3.000E+13 0.000 0.00 ! GRI1.2 CH2* + O = CO + H2 1.500E+13 0.000 0.00 ! GRI1.2 CH2* + O = HCO + H 1.500E+13 0.000 0.00 ! GRI1.2 CH2* + OH = CH2O + H 3.000E+13 0.000 0.00 ! GRI1.2 CH2* + H2 = CH3 + H 7.000E+13 0.000 0.00 ! GRI1.2 CH2* + O2 = H + OH + CO 2.800E+13 0.000 0.00 ! GRI1.2 CH2* + O2 = CO + H2O 1.200E+13 0.000 0.00 ! GRI1.2 CH2* + H2O(+M) = CH3OH(+M) 2.000E+13 0.000 0.00 ! GRI1.2 LOW / 2.700E+38 -6.300 3100.00/ TROE / 0.1507 134.00 2383.00 7265.00 / H2/2.0/ H2O/6.0/ CH4/2.0/ CO/1.5/ CO2/2.0/ C2H6/3.0/ C2H2/3.00/ C2H4/3.00/ CH2* + H2O = CH2 + H2O 3.000E+13 0.000 0.00 ! GRI1.2 CH2* + CO = CH2 + CO 9.000E+12 0.000 0.00 ! GRI1.2 CH2* + CO2 = CH2 + CO2 7.000E+12 0.000 0.00 ! GRI1.2 CH2* + CO2 = CH2O + CO 1.400E+13 0.000 0.00 ! GRI1.2 ! Reactions of CH2O CH2O + H(+M) = CH2OH(+M) 5.400E+11 0.454 3600.00 ! GRI1.2 LOW / 1.270E+32 -4.820 6530.00/ TROE/ 0.7187 103.00 1291.00 4160.00 / H2/2.0/ H2O/6.0/ CH4/2.0/ CO/1.5/ CO2/2.0/ C2H6/3.0/ C2H2/3.00/ C2H4/3.00/ CH2O + H(+M) = CH3O(+M) 5.400E+11 0.454 2600.00 ! GRI1.2 LOW / 2.200E+30 -4.800 5560.00/ TROE/ 0.7580 94.00 1555.00 4200.00 / H2/2.0/ H2O/6.0/ CH4/2.0/ CO/1.5/ CO2/2.0/ C2H6/3.0/ C2H2/3.00/ C2H4/3.00/ CH2O + H = HCO + H2 2.300E+10 1.050 3275.00 ! GRI1.2 CH2O + O = HCO + OH 3.900E+13 0.000 3540.00 ! GRI1.2 CH2O + OH = HCO + H2O 3.430E+09 1.180 -447.00 ! GRI1.2 CH2O + O2 = HCO + HO2 1.000E+14 0.000 40000.00 ! GRI1.2 CH2O + HO2 = HCO + H2O2 1.000E+12 0.000 8000.00 ! GRI1.2 CH2O + CH = CH2CO + H 9.460E+13 0.000 -515.00 ! GRI1.2 ! Reactions of CH3 CH3 + H(+M) = CH4(+M) 1.270E+16 -0.630 383.00 ! GRI1.2 LOW / 2.477E+33 -4.760 2440.00/ TROE/ 0.7830 74.00 2941.00 6964.00 / H2/2.0/ H2O/6.0/ CH4/2.0/ CO/1.5/ CO2/2.0/ C2H6/3.0/ AR/0.7/ C2H2/3.00/ C2H4/3.00/ CH3 + O = CH2O + H 8.430E+13 0.000 0.00 ! GRI1.2 CH3 + OH(+M) = CH3OH(+M) 6.300E+13 0.000 0.00 ! GRI1.2 LOW / 2.700E+38 -6.300 3100.00/ TROE/ 0.2105 83.50 5398.00 8370.00 / H2/2.0/ H2O/6.0/ CH4/2.0/ CO/1.5/ CO2/2.0/ C2H6/3.0/ C2H2/3.00/ C2H4/3.00/ CH3 + OH = CH2 + H2O 5.600E+07 1.600 5420.00 ! GRI1.2 CH3 + OH = CH2* + H2O 2.501E+13 0.000 0.00 ! GRI1.2 !CH3 + O2 = O + CH3O 2.675E+13 0.000 28800.00 ! GRI1.2 CH3 + O2 = O + CH3O 3.083E+13 0.000 28800.00 ! GRI-Mech 1.2a CH3 + O2 = OH + CH2O 3.600E+10 0.000 8940.00 ! GRI1.2 CH3 + HO2 = CH4 + O2 1.000E+12 0.000 0.00 ! GRI1.2 !CH3 + HO2 = CH3O + OH 2.000E+13 0.000 0.00 ! GRI1.2 CH3 + HO2 = CH3O + OH 1.340E+13 0.000 0.00 ! GRI-Mech 1.2a CH3 + H2O2 = CH4 + HO2 2.450E+04 2.470 5180.00 ! GRI1.2 CH3 + C = C2H2 + H 5.000E+13 0.000 0.00 ! GRI1.2 CH3 + CH = C2H3 + H 3.000E+13 0.000 0.00 ! GRI1.2 ! !CH3 + HCO = CH4 + CO 2.648E+13 0.000 0.00 ! GRI1.2 CH3 + HCO = CH4 + CO 8.480E+12 0.000 0.00 ! GRI1.2 - 1.8E13 for recombination CH3 + HCO (+M) = CH3CHO (+M) 1.800E+13 0.000 0.00 ! TS1, RRKM LOW / 2.200E+48 -9.588 5100.00 / TROE / 0.6173 13.076 2078. 5093. / H2/2.0/ H2O/6.0/ CH4/2.0/ CO/1.5/ CO2/2.0/ C2H6/3.0/ C2H2/3.00/ C2H4/3.00/ CH3 + CH2O = CH4 + HCO 3.320E+03 2.810 5860.00 ! GRI1.2 CH3 + CH2 = C2H4 + H 4.000E+13 0.000 0.00 ! GRI1.2 CH3 + CH2* = C2H4 + H 1.200E+13 0.000 -570.00 ! GRI1.2 CH3 + CH3(+M) = C2H6(+M) 2.120E+16 -0.970 620.00 ! GRI1.2 LOW / 1.770E+50 -9.670 6220.00/ TROE/ 0.5325 151.00 1038.00 4970.00 / H2/2.0/ H2O/6.0/ CH4/2.0/ CO/1.5/ CO2/2.0/ C2H6/3.0/ AR/0.7/ C2H2/3.00/ C2H4/3.00/ CH3 + CH3 = H + C2H5 4.990E+12 0.100 10600.00 ! GRI1.2 CH3 + HCCO = C2H4 + CO 5.000E+13 0.000 0.00 ! Est. HW AL CH3 + C2H = C3H3 + H 2.409E+13 0.000 0.00 ! 86TSA/HAM ! Reactions of CH3O/CH2OH CH3O + H(+M) = CH3OH(+M) 5.000E+13 0.000 0.00 ! GRI1.2 LOW / 8.600E+28 -4.000 3025.00/ TROE/ 0.8902 144.00 2838.00 45569.00 / H2/2.0/ H2O/6.0/ CH4/2.0/ CO/1.5/ CO2/2.0/ C2H6/3.0/ C2H2/3.00/ C2H4/3.00/ CH3O + H = CH2OH + H 3.400E+06 1.600 0.00 ! GRI1.2 CH3O + H = CH2O + H2 2.000E+13 0.000 0.00 ! GRI1.2 CH3O + H = CH3 + OH 3.200E+13 0.000 0.00 ! GRI1.2 CH3O + H = CH2* + H2O 1.600E+13 0.000 0.00 ! GRI1.2 CH3O + O = CH2O + OH 1.000E+13 0.000 0.00 ! GRI1.2 CH3O + OH = CH2O + H2O 5.000E+12 0.000 0.00 ! GRI1.2 CH3O + O2 = CH2O + HO2 4.280E-13 7.600 -3530.00 ! GRI1.2 CH2OH + H(+M) = CH3OH(+M) 1.800E+13 0.000 0.00 ! GRI1.2 LOW / 3.000E+31 -4.800 3300.00/ TROE/ 0.7679 338.00 1812.00 5081.00 / H2/2.0/ H2O/6.0/ CH4/2.0/ CO/1.5/ CO2/2.0/ C2H6/3.0/ C2H2/3.00/ C2H4/3.00/ CH2OH + H = CH2O + H2 2.000E+13 0.000 0.00 ! GRI1.2 CH2OH + H = CH3 + OH 1.200E+13 0.000 0.00 ! GRI1.2 CH2OH + H = CH2* + H2O 6.000E+12 0.000 0.00 ! GRI1.2 CH2OH + O = CH2O + OH 1.000E+13 0.000 0.00 ! GRI1.2 CH2OH + OH = CH2O + H2O 5.000E+12 0.000 0.00 ! GRI1.2 CH2OH + O2 = CH2O + HO2 1.800E+13 0.000 900.00 ! GRI1.2 ! Reactions of CH4 CH4 + H = CH3 + H2 6.600E+08 1.620 10840.00 ! GRI1.2 CH4 + O = CH3 + OH 1.020E+09 1.500 8600.00 ! GRI1.2 CH4 + OH = CH3 + H2O 1.000E+08 1.600 3120.00 ! GRI1.2 CH4 + CH = C2H4 + H 6.000E+13 0.000 0.00 ! GRI1.2 CH4 + CH2 = CH3 + CH3 2.460E+06 2.000 8270.00 ! GRI1.2 CH4 + CH2* = CH3 + CH3 1.600E+13 0.000 -570.00 ! GRI1.2 ! Reactions of CH3OH CH3OH + H = CH2OH + H2 1.700E+07 2.100 4870.00 ! GRI1.2 CH3OH + H = CH3O + H2 4.200E+06 2.100 4870.00 ! GRI1.2 CH3OH + O = CH2OH + OH 3.880E+05 2.500 3100.00 ! GRI1.2 CH3OH + O = CH3O + OH 1.300E+05 2.500 5000.00 ! GRI1.2 CH3OH + OH = CH2OH + H2O 1.440E+06 2.000 -840.00 ! GRI1.2 CH3OH + OH = CH3O + H2O 6.300E+06 2.000 1500.00 ! GRI1.2 CH3OH + CH3 = CH2OH + CH4 3.000E+07 1.500 9940.00 ! GRI1.2 CH3OH + CH3 = CH3O + CH4 1.000E+07 1.500 9940.00 ! GRI1.2 ! Reactions of C2H C2H + H(+M) = C2H2(+M) 1.000E+17 -1.000 0.00 ! GRI1.2 LOW / 3.750E+33 -4.800 1900.00/ TROE/ 0.6464 132.00 1315.00 5566.00 / H2/2.0/ H2O/6.0/ CH4/2.0/ CO/1.5/ CO2/2.0/ C2H6/3.0/ AR/0.7/ C2H2/3.00/ C2H4/3.00/ C2H + O = CH + CO 5.000E+13 0.000 0.00 ! GRI1.2 C2H + OH = H + HCCO 2.000E+13 0.000 0.00 ! GRI1.2 C2H + O2 = HCO + CO 5.000E+13 0.000 1500.00 ! GRI1.2 C2H + H2 = H + C2H2 4.900E+05 2.500 560.00 ! Wang & Frenklach !C2H + H2 = H + C2H2 4.070E+05 2.400 200.00 ! GRI1.2 ! Reactions of C2O C2O + H = CH + CO 5.000E+13 0.000 0.00 ! Miller-Melius C2O + O = CO + CO 5.000E+13 0.000 0.00 ! Miller-Melius C2O + OH = CO + CO + H 2.000E+13 0.000 0.00 ! Miller-Melius C2O + O2 = CO + CO + O 2.000E+13 0.000 0.00 ! Miller-Melius ! Reactions of HCCO HCCO + H = CH2* + CO 1.000E+14 0.000 0.00 ! GRI1.2 HCCO + O = H + CO + CO 1.000E+14 0.000 0.00 ! GRI1.2 HCCO + O2 = OH + 2CO 1.600E+12 0.000 854.00 ! GRI1.2 HCCO + CH = C2H2 + CO 5.000E+13 0.000 0.00 ! GRI1.2 HCCO + CH2 = C2H3 + CO 3.000E+13 0.000 0.00 ! GRI1.2 HCCO + HCCO = C2H2 + CO + CO 1.000E+13 0.000 0.00 ! GRI1.2 HCCO + OH = C2O + H2O 3.000E+13 0.000 0.00 ! Miller-Melius ! Reactions of C2H2 C2H2 (+M) = H2CC (+M) 8.000E+14 -0.520 50750.00 ! RRKM with 97.7 kcal/mol for H2CC LOW / 2.450E+15 -0.640 49700.00 / H2/2.0/ H2O/6.0/ CH4/2.0/ CO/1.5/ CO2/2.0/ C2H6/3.0/ C2H2/2.5/ C2H4/2.5/ !C2H2 + H(+M) = C2H3(+M) 5.600E+12 0.000 2400.00 ! GRI1.2 ! LOW / 3.800E+40 -7.270 7220.00/ ! TROE/ 0.7507 98.50 1302.00 4167.00 / ! H2/2.0/ H2O/6.0/ CH4/2.0/ CO/1.5/ CO2/2.0/ C2H6/3.0/ AR/0.7/ C2H2/2.5/ C2H4/2.5/ C2H3 (+M) = C2H2 + H (+M) 3.860E+08 1.620 37048.22 ! 96KNY/SLA, Zoran's Fc fit LOW / 2.565E+27 -3.400 35798.72/ TROE/ 1.9816 5383.7 4.2932 -0.0795 / H2/2.0/ H2O/6.0/ CH4/2.0/ CO/1.5/ CO2/2.0/ C2H6/3.0/ AR/0.7/ C2H2/3.00/ C2H4/3.00/ C2H2 + O = C2H + OH 4.600E+19 -1.410 28950.00 ! GRI1.2 C2H2 + O = HCCO + H 1.632E+07 2.000 1900.00 ! GRI1.2, alpha = 0.8 Michael & Wagner C2H2 + O = CH2 + CO 4.080E+06 2.000 1900.00 ! GRI1.2, alpha = 0.2 C2H2 + OH = CH2CO + H 2.180E-04 4.500 -1000.00 ! GRI1.2 C2H2 + OH = HCCOH + H 5.040E+05 2.300 13500.00 ! GRI1.2 C2H2 + OH = C2H + H2O 3.370E+07 2.000 14000.00 ! GRI1.2 C2H2 + OH = CH3 + CO 4.830E-04 4.000 -2000.00 ! GRI1.2 C2H2 + HCO = C2H3 + CO 1.000E+07 2.000 6000.00 ! Estimated C2H2 + CH = C3H2 + H 3.000E+13 0.000 0.00 ! 83WAR C2H2 + CH2 = C3H3 + H 1.200E+13 0.000 6620.00 ! 88BOH/TEM; 86FRA/BHA !C2H2 + CH2* = C3H3 + H 2.000E+14 0.000 0.00 ! 86FRA/BHA C2H2 + CH2* = C3H3 + H 2.000E+13 0.000 0.00 ! Wang and Frenklach C2H2 + C2H = C4H2 + H 9.600E+13 0.000 0.00 ! 91SHI/MIC, 92KOS/FUK, 93FAR/MOR ! C2H2 + C2H (+M) = n-C4H3 (+M) 8.300E+10 0.899 -363.00 ! RRKM LOW /1.240E+31 -4.718 1871.00 / TROE /1.0 100. 5613. 13387. / H2/2.0/ H2O/6.0/ CH4/2.0/ CO/1.5/ CO2/2.0/ C2H6/3.0/ C2H2/2.5/ C2H4/2.5/ C2H2 + C2H (+M) = i-C4H3 (+M) 8.300E+10 0.899 -363.00 ! RRKM LOW /1.240E+31 -4.718 1871.00 / TROE /1.0 100. 5613. 13387. / H2/2.0/ H2O/6.0/ CH4/2.0/ CO/1.5/ CO2/2.0/ C2H6/3.0/ C2H2/2.5/ C2H4/2.5/ C2H2 + HCCO = C3H3 + CO 1.000E+11 0.000 3000.00 ! Miller-Bowman;83HOM/WEL2 C2H2 + CH3 = pC3H4 + H 2.560E+09 1.100 13644.00 ! WD RRKM very little P dependence (k at 1 atm) C2H2 + CH3 = aC3H4 + H 5.140E+09 0.860 22153.00 ! WD RRKM very little P dependence (k at 1 atm) C2H2 + CH3 + M = CH3CCH2 + M 4.000E+24 -3.390 18840.00 ! WD RRKM p < 10 atm, T > 500 K, low-p limit C2H2 + CH3 + M = aC3H5 + M 2.200E+55 -11.820 35730.00 ! WD RRKM p < 10 atm, T > 500 K, low-p limit !C2H2 + CH3 = CH3CHCH 1.400E+32 -7.140 10000.00 ! RRKM 76 Torr C2H2 + CH3 = CH3CHCH 3.200E+35 -7.760 13300.00 ! RRKM 760 Torr !C2H2 + CH3 = CH3CHCH 2.400E+38 -8.210 17100.00 ! RRKM 7600 Torr ! Reactions of Vinylidene H2CC + H = C2H2 + H 1.000E+14 0.000 0.00 ! Estimated H2CC + O = CH2 + CO 1.000E+14 0.000 0.00 ! Estimated H2CC + OH = CH2CO + H 2.000E+13 0.000 0.00 ! Estimated H2CC + O2 = CO2 + CH2 1.000E+13 0.000 0.00 ! Estimated ! H2CC + C2H2 (+M) = C4H4 (+M) 3.500E+05 2.055 -2400.00 ! RRKM * 0.8 LOW /1.400E+60 -12.599 7417.00 / TROE /0.980 56.0 580.0 4164.0 / H2/2.0/ H2O/6.0/ CH4/2.0/ CO/1.5/ CO2/2.0/ C2H6/3.0/ C2H2/3.00/ C2H4/3.00/ ! Reactions of CH2CO/HCCOH CH2CO + H (+M) = CH2CHO (+M) 3.300E+14 -0.060 8500.00 ! kinf, RRKM, Ko for He LOW /3.800E+41 -7.640 11900.00 / TROE /0.337 1707. 3200. 4131. / H2/2/ H2O/6/ CH4/2/ CO/1.5/ CO2/2/ C2H6/3/ AR/0.7/ C2H2/3.00/ C2H4/3.00/ CH2CO + H = HCCO + H2 5.000E+13 0.000 8000.00 ! GRI1.2 !CH2CO + H = CH3 + CO 1.130E+13 0.000 3428.00 ! GRI1.2 CH2CO + H = CH3 + CO 1.500E+09 1.430 2690.00 ! RRKM, vista CH2CO + O = HCCO + OH 1.000E+13 0.000 8000.00 ! GRI1.2 CH2CO + O = CH2 + CO2 1.750E+12 0.000 1350.00 ! GRI1.2 CH2CO + OH = HCCO + H2O 7.500E+12 0.000 2000.00 ! GRI1.2 HCCOH + H = CH2CO + H 1.000E+13 0.000 0.00 ! GRI1.2 ! Reactions of C2H3 C2H3 + H(+M) = C2H4(+M) 6.080E+12 0.270 280.00 ! GRI1.2 LOW / 1.400E+30 -3.860 3320.00/ TROE/ 0.7820 207.50 2663.00 6095.00 / H2/2.0/ H2O/6.0/ CH4/2.0/ CO/1.5/ CO2/2.0/ C2H6/3.0/ AR/0.7/ C2H2/3.00/ C2H4/3.00/ C2H3 + H = C2H2 + H2 3.000E+13 0.000 0.00 ! GRI1.2 C2H3 + H = H2CC + H2 6.000E+13 0.000 0.00 ! Estmated (Chemically activated) !C2H3 + O = CH2CO + H 3.000E+13 0.000 0.00 ! GRI1.2 C2H3 + O = CH2CO + H 4.800E+13 0.000 0.00 ! 86TSA/HAM, alpha = 0.5 C2H3 + O = CH3 + CO 4.800E+13 0.000 0.00 ! 86TSA/HAM, alpha = 0.5, Donaldson et al. !C2H3 + OH = C2H2 + H2O 5.000E+12 0.000 0.00 ! GRI1.2 C2H3 + OH = C2H2 + H2O 3.011E+13 0.000 0.00 ! 86TSA/HAM ! C2H3 + O2 = C2H2 + HO2 1.340E+06 1.610 -383.40 ! 96MEB/DIA, 1 atm, negligible p dependence C2H3 + O2 = CH2CHO + O 3.000E+11 0.290 11.00 ! 96MEB/DIA, 1 atm, negligible p dependence C2H3 + O2 = HCO + CH2O 4.600E+16 -1.390 1010.00 ! 96MEB/DIA, 1 atm, negligible p dependence !C2H3 + O2 = HCO + CH2O 3.980E+12 0.000 -240.00 ! GRI1.2, 84SLA/PAR C2H3 + HO2 = CH2CHO + OH 1.000E+13 0.000 0.00 ! Estimated ! C2H3 + H2O2 = C2H4 + HO2 1.210E+10 0.000 -596.00 ! Tsang Hampson 1 C2H3 + HCO = C2H4 + CO 9.033E+13 0.000 0.00 ! 86TSA/HAM C2H3 + CH3 = C2H2 + CH4 3.920E+11 0.000 0.00 ! Tsang Hampson 1 C2H3 + CH3 (+M) = C3H6(+M) 2.500E+13 0.000 0.00 ! TS1 600cm-1 LOW / 4.270E+58 -11.940 9769.80/ TROE / 0.175 1340.6 60000.0 10139.8 / H2/2/ H2O/6/ CH4/2/ CO/1.5/ CO2/2/ C2H6/3/ AR/0.7/ C2H2/3.00/ C2H4/3.00/ C2H3 + CH3 = aC3H5 + H 1.500E+24 -2.830 18618.00 ! TS1 1 atm, but need to be further examined C2H3 + C2H2 = C4H4 + H 5.000E+14 -0.710 6700.00 ! RRKM at 0.263 atm, small p dependence <10 atm ! Reactions of CH2CHO !CH2CHO = CH3 + CO 2.340E+43 -10.099 45600.00 ! RRKM 20 Torr !CH2CHO = CH3 + CO 8.000E+43 -10.058 46500.00 ! RRKM 76 Torr !CH2CHO = CH3 + CO 7.200E+42 -9.521 47000.00 ! RRKM 380 Torr CH2CHO = CH3 + CO 7.800E+41 -9.147 46900.00 ! RRKM 760 Torr !CH2CHO = CH3 + CO 4.800E+40 -8.704 46800.00 ! RRKM 1520 Torr !CH2CHO = CH3 + CO 7.500E+39 -8.416 46680.00 ! RRKM 2280 Torr !CH2CHO = CH3 + CO 1.800E+39 -8.200 46600.00 ! RRKM 3040 Torr !CH2CHO = CH3 + CO 5.640E+38 -8.027 46470.00 ! RRKM 3800 Torr !CH2CHO = CH3 + CO 2.120E+38 -7.881 46390.00 ! RRKM 4560 Torr !CH2CHO = CH3 + CO 9.000E+37 -7.755 46310.00 ! RRKM 5320 Torr !CH2CHO = CH3 + CO 4.200E+37 -7.644 46240.00 ! RRKM 6080 Torr !CH2CHO = CH3 + CO 1.200E+37 -7.456 46100.00 ! RRKM 7600 Torr CH2CHO + H (+M) = CH3CHO (+M) 1.000E+14 0.000 0.00 ! Estimated, RRKM LOW /5.200E+39 -7.297 4700.00 / TROE /0.55 8900. 4350. 7244. / H2/2/ H2O/6/ CH4/2/ CO/1.5/ CO2/2/ C2H6/3/ C2H2/3.00/ C2H4/3.00/ CH2CHO + H = CH3CO + H 5.000E+12 0.000 0.00 ! RRKM, *2/2 CH2CHO + H = CH3 + HCO 9.000E+13 0.000 0.00 ! RRKM, *1.2 /3 CH2CHO + H = CH2CO + H2 2.000E+13 0.000 4000.00 ! 82MIL/MIT CH2CHO + O = CH2CO + OH 2.000E+13 0.000 4000.00 ! 82MIL/MIT CH2CHO + OH = CH2CO + H2O 1.000E+13 0.000 2000.00 ! 82MIL/MIT CH2CHO + O2 = CH2CO + HO2 1.400E+11 0.000 0.00 ! Baulch et al 1994 CH2CHO + O2 = CH2O + CO + OH 1.800E+10 0.000 0.00 ! Baulch et al 1994 ! Reactions of CH3CO CH3 + CO (+M) = CH3CO (+M) 4.850E+07 1.650 6150.00 ! kinf, RRKM, k0 for He LOW /7.800E+30 -5.395 8600.00 / TROE /0.258 598. 21002. 1773. / H2/2/ H2O/6/ CH4/2/ CO/1.5/ CO2/2/ C2H6/3/ AR/0.7/ C2H2/3.00/ C2H4/3.00/ CH3CO + H (+M) = CH3CHO (+M) 9.600E+13 0.000 0.00 ! TS1, RRKM LOW /3.850E+44 -8.569 5500.00 / TROE /1.0000 2900. 2900. 5132./ H2/2/ H2O/6/ CH4/2/ CO/1.5/ CO2/2/ C2H6/3/ C2H2/3.00/ C2H4/3.00/ CH3CO + H = CH3 + HCO 8.000E+13 0.000 0.00 ! RRKM CH3CO + O = CH2CO + OH 3.900E+13 0.000 0.00 ! CEC CH3CO + O = CH3 + CO2 1.500E+14 0.000 0.00 ! CEC + TS1 CH3CO + OH = CH2CO + H2O 1.200E+13 0.000 0.00 ! TS1 CH3CO + OH = CH3 + CO + OH 3.000E+13 0.000 0.00 ! TS1 CH3CO + HO2 = CH3 + CO2 + OH 3.000E+13 0.000 0.00 ! TS1 CH3CO + H2O2 = CH3CHO + HO2 1.800E+11 0.000 8226.00 ! TS1 ! Reactions of CH3CHO CH3CHO + O2 = CH3CO + HO2 3.000E+13 0.000 39100.00 ! Baulch et al 1994 CH3CHO + OH = CH3CO + H2O 2.350E+10 0.730 -1110.00 ! Baulch et al 1994 CH3CHO + H = CH3CO + H2 4.100E+09 1.160 2400.00 ! Baulch et al 1994 CH3CHO + O = CH3CO + OH 5.800E+12 0.000 1800.00 ! Baulch et al 1994 CH3CHO + CH3 = CH3CO + CH4 2.000E-06 5.600 2460.00 ! Baulch et al 1994 ! Reactions of C2H4 C2H4(+M) = H2 + H2CC(+M) 8.000E+12 0.440 88770.00 ! GRI1.2 LOW / 7.000E+50 -9.310 99860.00/ TROE/ 0.7345 180.00 1035.00 5417.00 / H2/2.0/ H2O/6.0/ CH4/2.0/ CO/1.5/ CO2/2.0/ C2H6/3.0/ AR/0.7/ C2H2/3.00/ C2H4/3.00/ C2H4 + H(+M) = C2H5(+M) 1.080E+12 0.454 1820.00 ! GRI1.2 LOW / 1.200E+42 -7.620 6970.00/ TROE/ 0.9753 210.00 984.00 4374.00 / H2/2.0/ H2O/6.0/ CH4/2.0/ CO/1.5/ CO2/2.0/ C2H6/3.0/ AR/0.7/ C2H2/3.00/ C2H4/3.00/ !C2H4 + H = C2H3 + H2 1.325E+06 2.530 12240.00 ! GRI1.2 C2H4 + H = C2H3 + H2 5.070E+07 1.930 12950.00 ! 96KNY/BEN C2H4 + O = OH + C2H3 1.510E+07 1.910 3740.00 ! 87MAH/MAR C2H4 + O = CH3 + HCO 1.920E+07 1.830 220.00 ! GRI 1.2 C2H4 + O = CH2 + CH2O 3.840E+05 1.830 220.00 ! 2% GRI-Mech, Estimated for CH2 production C2H4 + OH = C2H3 + H2O 3.600E+06 2.000 2500.00 ! GRI1.2 C2H4 + O2 = C2H3 + HO2 4.220E+13 0.000 60800.00 ! Tsang-Hampson1+3.2 kcal/mol C2H4 + HO2 = CH3CHO + OH 2.000E+12 0.000 14000.00 ! Estimated (QM in progress) C2H4 + HCO = C2H5 + CO 1.000E+07 2.000 8000.00 ! Estimated C2H4 + CH = aC3H4 + H 3.000E+13 0.000 0.00 ! Estimated C2H4 + CH = pC3H4 + H 3.000E+13 0.000 0.00 ! Estimated C2H4 + CH2 = aC3H5 + H 2.000E+13 0.000 6000.00 ! Estimated C2H4 + CH2* = H2CC + CH4 5.000E+13 0.000 0.00 ! Estimated C2H4 + CH2* = aC3H5 + H 5.000E+13 0.000 0.00 ! Estimated C2H4 + CH3 = C2H3 + CH4 2.270E+05 2.000 9200.00 ! GRI1.2 C2H4 + CH3 = nC3H7 3.300E+11 0.000 7700.0 ! KP C2H4 + C2H = C4H4 + H 1.200E+13 0.000 0.00 ! Tsang Hampson 1 ! Reactions of C2H5 C2H5 + H(+M) = C2H6(+M) 5.210E+17 -0.990 1580.00 ! GRI1.2 LOW / 1.990E+41 -7.080 6685.00/ TROE/ 0.8422 125.00 2219.00 6882.00 / H2/2.0/ H2O/6.0/ CH4/2.0/ CO/1.5/ CO2/2.0/ C2H6/3.0/ AR/0.7/ C2H2/3.00/ C2H4/3.00/ C2H5 + H = C2H4 + H2 2.000E+12 0.000 0.00 ! GRI1.2 !C2H5 + O = CH3 + CH2O 1.320E+14 0.000 0.00 ! GRI1.2 C2H5 + O = CH3 + CH2O 1.604E+13 0.000 0.00 ! 86TSA/HAM C2H5 + O = CH3CHO + H 8.020E+13 0.000 0.00 ! 86TSA/HAM !C2H5 + O2 = C2H4 + HO2 8.400E+11 0.000 3875.00 ! GRI1.2 C2H5 + O2 = C2H4 + HO2 2.000E+10 0.000 0.00 ! Based on Bozzelli (avoid pressure dependence) C2H5 + HO2 = C2H6 + O2 3.000E+11 0.000 0.00 ! TS1 C2H5 + HO2 = C2H4 + H2O2 3.000E+11 0.000 0.00 ! TS1 C2H5 + HO2 = CH3 + CH2O + OH 2.400E+13 0.000 0.00 ! TS1 C2H5 + H2O2 = C2H6 + HO2 8.700E+09 0.000 974.00 ! TS1 C2H5 + HCO = C2H6 + CO 1.200E+14 0.000 0.00 ! TS1 ! Reactions of C2H6 C2H6 + H = C2H5 + H2 1.150E+08 1.900 7530.00 ! GRI1.2 C2H6 + O = C2H5 + OH 8.980E+07 1.920 5690.00 ! GRI1.2 C2H6 + OH = C2H5 + H2O 3.540E+06 2.120 870.00 ! GRI1.2 C2H6 + CH2* = C2H5 + CH3 4.000E+13 0.000 -550.00 ! GRI1.2 C2H6 + CH3 = C2H5 + CH4 6.140E+06 1.740 10450.00 ! GRI1.2 ! Reactions of C3H2 C3H2 + O = C2H2 + CO 6.80E+13 0.0 0.0 ! Warnatz 82 C3H2 + OH = HCO + C2H2 6.80E+13 0.0 0.0 ! War82 Prod/Miller C3H2 + O2 = HCCO + H + CO 2.00E+12 0.0 1000.0 ! Miller C3H2 + CH = C4H2 + H 5.00E+13 0.0 0.0 ! Estimated C3H2 + CH2 = n-C4H3 + H 5.00E+13 0.0 0.0 ! Estimated C3H2 + CH3 = C4H4 + H 5.00E+12 0.0 0.0 ! Estimated C3H2 + HCCO = n-C4H3 + CO 1.00E+13 0.0 0.0 ! Estimated C3H2 + H = C3H3 1.00E+13 0.0 0.0 ! Estimated ! Reactions of C3H3 C3H3 + H = pC3H4 1.500E+13 0.0 0.0 ! Est. C3H3 + H = aC3H4 2.500E+12 0.0 0.0 ! Est. C3H3 + H = C3H2 + H2 5.00E+13 0.0 1000.0 ! Miller C3H3 + O = CH2O + C2H 2.00E+13 0.0 0.0 ! Miller-Bowman C3H3 + OH = C3H2 + H2O 2.00E+13 0.0 0.0 ! Miller-Bowman C3H3 + O2 = CH2CO + HCO 3.00E+10 0.0 2868.0 ! Gutman C3H3 + HO2 = OH + CO + C2H3 8.00E+11 0.0 0.0 ! Estimated C3H3 + HO2 = aC3H4 + O2 3.00E+11 0.0 0.0 ! EST-NEW C3H3 + HO2 = pC3H4 + O2 2.50E+12 0.0 0.0 ! EST-NEw C3H3 + HCO = aC3H4 + CO 2.50E+13 0.0 0.0 ! Estimated C3H3 + HCO = pC3H4 + CO 2.50E+13 0.0 0.0 ! Estimated C3H3 + HCCO = C4H4 + CO 2.50E+13 0.0 0.0 ! Estimated C3H3 + CH = i-C4H3 + H 5.00E+13 0.0 0.0 ! Estimated C3H3 + CH2 = C4H4 + H 5.00E+13 0.0 0.0 ! Estimated i-C4H5 + H = C3H3 + CH3 2.00E+13 0.0 2000.0 ! Estimated C3H3 + CH3 (+M) = C4H612 (+M) 1.50E+12 0.0 0.0 ! kinf assumed falloff=C2H3+CH3 TS1 600 cm-1 LOW /2.60E+57 -11.94 9770.0/ TROE /0.175 1340.6 60000.0 9769.8/ H2/2.0/ H2O/6.0/ CH4/2.0/ CO/1.5/ CO2/2.0/ C2H6/3.0/ AR/0.7/ C3H3 + C3H3 =>A1- + H 5.000E+12 0.0 0.0 ! Davis, Law, Wang C3H3 + C3H3 = A1 2.000E+12 0.0 0.0 ! Davis, Law, Wang ! Isomerizations of aC3H4, pC3H4 and cC3H4 pC3H4 (+M) = cC3H4 (+M) 1.800E+12 0.309 60000.00 ! RRKM, kinf LOW /1.890E+45 -8.871 64200.00 / TROE /0.174 1084.0 20000.0 4267. / H2/2.0/ H2O/6.0/ CH4/2.0/ CO/1.5/ CO2/2.0/ C2H6/3.0/ C2H2/3.00/ C2H4/3.00/ cC3H4 (+M) = aC3H4 (+M) 1.800E+12 0.578 42200.00 ! RRKM, kinf LOW /4.000E+46 -9.112 46900.00 / TROE / 0.0 236. 2000. 1594. / H2/2.0/ H2O/6.0/ CH4/2.0/ CO/1.5/ CO2/2.0/ C2H6/3.0/ C2H2/3.00/ C2H4/3.00/ !pC3H4 = aC3H4 2.359E+56 -13.392 81554.61 ! RRKM 10 Torr !pC3H4 = aC3H4 1.053E+56 -13.191 82018.08 ! RRKM 20 Torr !pC3H4 = aC3H4 6.119E+54 -12.646 82727.50 ! RRKM 76 Torr !pC3H4 = aC3H4 4.310E+52 -11.803 83520.36 ! RRKM 380 Torr pC3H4 = aC3H4 3.727E+51 -11.401 83917.21 ! RRKM 760 Torr !pC3H4 = aC3H4 2.531E+50 -10.971 84338.60 ! RRKM 1520 Torr !pC3H4 = aC3H4 4.509E+49 -10.701 84585.20 ! RRKM 2280 Torr !pC3H4 = aC3H4 1.195E+49 -10.497 84749.30 ! RRKM 3040 Torr !pC3H4 = aC3H4 4.021E+48 -10.332 84870.04 ! RRKM 3800 Torr !pC3H4 = aC3H4 1.570E+48 -10.190 84960.82 ! RRKM 4560 Torr !pC3H4 = aC3H4 6.879E+47 -10.068 85033.40 ! RRKM 5320 Torr !pC3H4 = aC3H4 3.257E+47 -9.957 85090.13 ! RRKM 6080 Torr !pC3H4 = aC3H4 1.641E+47 -9.857 85135.24 ! RRKM 6840 Torr !pC3H4 = aC3H4 8.787E+46 -9.766 85174.06 ! RRKM 7600 Torr ! Reactions of aC3H4 aC3H4 + H = C3H3 + H2 1.300E+06 2.000 5500.00 ! = pC3H4 + H Est HW aC3H4 + H + M = CH3CCH2 + M 7.760E+44 -8.430 11190.00 ! WD, RRKM, not a low-p limit, but adequate H2/2.0/ H2O/6.0/ CH4/2.0/ CO/1.5/ CO2/2.0/ C2H6/3.0/ C2H2/3.00/ C2H4/3.00/ aC3H4 + H (+M) = aC3H5 (+M) 3.380E+09 1.477 4786.00 ! WD RRKM 300-2500 K LOW /7.500E+59 -12.484 13678.00 / TROE /0.0 650.0 1000.0 3496.1 / H2/2.0/ H2O/6.0/ CH4/2.0/ CO/1.5/ CO2/2.0/ C2H6/3.0/ C2H2/3.00/ C2H4/3.00/ aC3H4 + O = C2H4 + CO 2.000E+07 1.800 1000.00 ! Est. See notes (HW) aC3H4 + OH = C3H3 + H2O 5.300E+06 2.000 2000.00 ! Refit to Liu(88LIU/MUL) aC3H4 + CH3 = C3H3 + CH4 1.300E+12 0.00 7700.0 ! lowered by ~30% from Wu & Kern/KER aC3H4 + C2H = C2H2 + C3H3 1.000E+13 0.000 0.00 ! 87WU/KER aC3H4 + A1- = A1 + C3H3 2.000E+12 0.0 15000.0 ! Davis, Law, Wang ! Reactions of pC3H4 pC3H4 + H = aC3H4 + H 6.270E+17 -0.910 10079.00 ! WD p dependence below 1000 K pC3H4 + H + M = CH3CCH2 + M 1.360E+49 -9.580 13690.00 ! WD good for T > 1000 K !pC3H4 + H = CH3CHCH 1.000E+25 -5.000 1800.00 ! RRKM 76 Torr pC3H4 + H = CH3CHCH 5.500E+28 -5.74 4300.00 ! RRKM 760 Torr !pC3H4 + H = CH3CHCH 1.000E+34 -6.880 8900.00 ! RRKM 7600 Torr !pC3H4 + H = aC3H5 1.156E+57 -14.043 24219.62 ! RRKM 10 Torr !pC3H4 + H = aC3H5 5.334E+57 -14.123 25183.21 ! RRKM 20 Torr !pC3H4 + H = aC3H5 1.797E+58 -14.060 26813.30 ! RRKM 76 Torr !pC3H4 + H = aC3H5 6.141E+57 -13.669 28504.93 ! RRKM 380 Torr pC3H4 + H = aC3H5 2.074E+57 -13.423 29212.92 ! RRKM 760 Torr !pC3H4 + H = aC3H5 4.991E+56 -13.135 29923.81 ! RRKM 1520 Torr !pC3H4 + H = aC3H5 1.824E+56 -12.946 30337.02 ! RRKM 2280 Torr !pC3H4 + H = aC3H5 8.106E+55 -12.799 30624.11 ! RRKM 3040 Torr !pC3H4 + H = aC3H5 4.097E+55 -12.679 30843.41 ! RRKM 3800 Torr !pC3H4 + H = aC3H5 2.232E+55 -12.575 31015.57 ! RRKM 4560 Torr !pC3H4 + H = aC3H5 1.301E+55 -12.484 31160.08 ! RRKM 5320 Torr !pC3H4 + H = aC3H5 7.897E+54 -12.401 31279.79 ! RRKM 6080 Torr !pC3H4 + H = aC3H5 4.988E+54 -12.325 31382.95 ! RRKM 6840 Torr !pC3H4 + H = aC3H5 3.231E+54 -12.255 31471.23 ! RRKM 7600 Torr ! pC3H4 + H = C3H3 + H2 1.300E+06 2.000 5500.00 ! Estimated (from Wu and Kern) pC3H4 + O = HCCO + CH3 0.730E+13 0.000 2250.00 ! Fontijn/split pC3H4 + O = C2H4 + CO 1.000E+13 0.000 2250.00 ! Fontijn/split (+74HER/WAG) pC3H4 + O = C3H3 + OH 3.450E+04 2.160 4830.00 ! Fontijn pC3H4 + OH = C3H3 + H2O 1.000E+06 2.000 100.00 ! This work pC3H4 + CH3 = C3H3 + CH4 1.800E+12 0.000 7700.00 ! Wu & Kern pC3H4 + C2H = C2H2 + C3H3 1.000E+13 0.000 0.00 ! Estimated pC3H4 + A1- = C3H3 + A1 2.000E+12 0.000 15000.00 ! Davis, Law, Wang ! Reactions of allyl (aC3H5) aC3H5 + H(+M) = C3H6(+M) 2.000E+14 0.000 0.00 ! TS5 600cm-1 LOW / 1.330E+60 -12.000 5967.80/ TROE / 0.020 1096.6 1096.6 6859.5 / H2/2/ H2O/6/ CH4/2/ CO/1.5/ CO2/2/ C2H6/3/ AR/0.7/ C2H2/3.00/ C2H4/3.00/ aC3H5 + H = aC3H4 + H2 1.800E+13 0.000 0.00 ! TS5 k(c) aC3H5 + H = H2CC + CH4 2.000E+13 0.000 2000.00 ! Estimated aC3H5 + O = C2H3CHO + H 6.000E+13 0.000 0.00 ! TS5 aC3H5 + OH = C2H3CHO + H + H 4.200E+32 -5.160 30126.00 ! TS5, 1 atm, mild p dependence between 0.1 - 10 atm aC3H5 + OH = aC3H4 + H2O 6.000E+12 0.000 0.00 ! TS5 k(a) aC3H5 + O2 = aC3H4 + HO2 4.990E+15 -1.400 22428.00 ! Bozzelli, little p dependence at high T aC3H5 + O2 = CH3CO + CH2O 1.190E+15 -1.010 20128.00 ! Bozzelli, little p dependence aC3H5 + O2 = C2H3CHO + OH 1.820E+13 -0.410 22859.00 ! Bozzelli, little p dependence aC3H5 + HO2 = C3H6 + O2 2.660E+12 0.000 0.00 ! CEC aC3H5 + HO2 = OH + C2H3 + CH2O 6.600E+12 0.000 0.00 ! CEC aC3H5 + HCO = C3H6 + CO 6.000E+13 0.00 0.00 ! TS5 aC3H5+CH3(+M) = C4H81(+M) 1.00E+14 -0.32 -262.3 ! TS5 300CM-1 LOW / 3.51E+60 -12.97 6000.0 / TROE / 0.896 60000.0 1606.0 6118.4 / H2/2/ H2O/6/ CH4/2/ CO/1.5/ CO2/2/ C2H6/3/ AR/0.7/ aC3H5 + CH3 = aC3H4 + CH4 3.000E+12 -0.32 -131.00 ! TS5 k(a) !aC3H5 = CH3CCH2 2.887E+68 -17.661 77527.69 ! RRKM 10 Torr !aC3H5 = CH3CCH2 7.918E+67 -17.399 77863.49 ! RRKM 20 Torr !aC3H5 = CH3CCH2 1.236E+66 -16.702 78168.75 ! RRKM 76 Torr !aC3H5 = CH3CCH2 6.564E+63 -15.857 78672.74 ! RRKM 380 Torr aC3H5 = CH3CCH2 9.440E+62 -15.537 79079.65 ! RRKM 760 Torr !aC3H5 = CH3CCH2 1.379E+62 -15.221 79569.93 ! RRKM 1520 Torr !aC3H5 = CH3CCH2 4.090E+61 -15.027 79870.07 ! RRKM 2280 Torr !aC3H5 = CH3CCH2 1.575E+61 -14.878 80074.33 ! RRKM 3040 Torr !aC3H5 = CH3CCH2 7.094E+60 -14.756 80225.79 ! RRKM 3800 Torr !aC3H5 = CH3CCH2 3.507E+60 -14.650 80341.20 ! RRKM 4560 Torr !aC3H5 = CH3CCH2 1.861E+60 -14.555 80432.06 ! RRKM 5320 Torr !aC3H5 = CH3CCH2 1.044E+60 -14.470 80505.48 ! RRKM 6080 Torr !aC3H5 = CH3CCH2 6.141E+59 -14.393 80566.55 ! RRKM 6840 Torr !aC3H5 = CH3CCH2 3.732E+59 -14.320 80616.31 ! RRKM 7600 Torr !aC3H5 = CH3CHCH 1.300E+55 -14.530 73800.00 ! RRKM 76 Torr aC3H5 = CH3CHCH 5.000E+51 -13.020 73300.00 ! RRKM 760 Torr !aC3H5 = CH3CHCH 9.700E+48 -11.730 73700.00 ! RRKM 7600 Torr ! Reactions of propen-2-yl (sC3H5) CH3CCH2 + H = pC3H4 + H2 3.340E+12 0.000 0.00 ! PW CH3CCH2 + H = aC3H5 + H 5.000E+13 0.000 0.00 ! Est. CH3CCH2 + O = CH3 + CH2CO 6.000E+13 0.000 0.00 ! Est. HW CH3CCH2 + OH = CH3 + CH2CO + H 5.000E+12 0.000 0.00 ! Est. HW CH3CCH2 + O2 = CH3CO + CH2O 1.000E+11 0.000 0.00 ! Davis, Law, Wang CH3CCH2 + HO2 = CH3 + CH2CO + OH 2.000E+13 0.000 0.00 ! Est. HW CH3CCH2 + HCO = C3H6 + CO 9.000E+13 0.000 0.00 ! Est. HW CH3CCH2 + CH3 = pC3H4 + CH4 1.000E+11 0.000 0.00 ! PW !CH3CCH2 = CH3CHCH 1.600E+44 -12.160 52200.00 ! RRKM 76 Torr CH3CCH2 = CH3CHCH 1.500E+48 -12.710 53900.00 ! RRKM 760 Torr !CH3CCH2 = CH3CHCH 5.100E+52 -13.370 57200.00 ! RRKM 7600 Torr ! Reactions of propen-1-yl (tC3H5) CH3CHCH + H = pC3H4 + H2 3.340E+12 0.000 0.00 ! Est. CH3CHCH + H = aC3H5 + H 5.000E+13 0.000 0.00 ! Est. CH3CHCH + O = C2H5 + CO 6.000E+13 0.000 0.00 ! Est. HW CH3CHCH + OH = C2H5 + CO + H 5.000E+12 0.000 0.00 ! Est. HW CH3CHCH + O2 = CH3CHO + HCO 1.000E+11 0.000 0.00 ! Davis, Law, Wang CH3CHCH + HO2 = C2H5 + CO + OH 2.000E+13 0.000 0.00 ! Est. HW CH3CHCH + HCO = C3H6 + CO 9.000E+13 0.000 0.00 ! Est. HW CH3CHCH + CH3 = pC3H4 + CH4 1.000E+11 0.000 0.00 ! PW ! Reactions of C2H3CHO C2H3 + HCO = C2H3CHO 1.800E+13 0.000 0.00 ! TS5 C2H3CHO + H = C2H4 + HCO 1.080E+12 0.454 1820.00 ! = C2H4 + H (kinf) C2H3CHO + O = C2H3 + OH + CO 3.000E+13 0.000 3540.00 ! = CH2O + O C2H3CHO + O = CH2O + CH2CO 1.900E+07 1.800 220.00 ! = C2H4 + O C2H3CHO + OH = C2H3 + H2O + CO 3.430E+09 1.180 -447.00 ! = CH2O + OH ! Reactions of propene (C3H6) C3H6+H(+M) = nC3H7(+M) 1.33E+13 0.00 3260.7 ! TS5 600 cm-1 LOW / 6.26E+38 -6.66 7000.0 / TROE / 1.000 1000.0 1310.0 48097.0 / H2/2/ H2O/6/ CH4/2/ CO/1.5/ CO2/2/ C2H6/3/ AR/0.7/ C3H6+H(+M) = iC3H7(+M) 1.33E+13 0.00 1559.8 ! TS5 600cm-1 LOW / 8.70E+42 -7.50 4721.8 / TROE / 1.000 1000.0 645.4 6844.3 / H2/2/ H2O/6/ CH4/2/ CO/1.5/ CO2/2/ C2H6/3/ AR/0.7/ C3H6 + H = C2H4 + CH3 1.600E+22 -2.390 11180.00 ! TS5 1 atm little p dependence above 1000 K C3H6 + H = aC3H5 + H2 1.700E+05 2.500 2490.00 ! TS5 k(a) C3H6 + H = CH3CCH2 + H2 4.000E+05 2.500 9790.00 ! TS5 k(b) C3H6 + H = CH3CHCH + H2 8.000E+05 2.500 12280.00 ! TS5 k(c) C3H6 + O = CH2CO + CH3 + H 1.200E+08 1.650 327.00 ! TS5 k(a+b) tot C3H6 + O = C2H5 + HCO 3.500E+07 1.650 -972.00 ! TS5 k(c) C3H6 + O = aC3H5 + OH 1.800E+11 0.700 5880.00 ! TS5 k(d) C3H6 + O = CH3CCH2 + OH 6.000E+10 0.700 7630.00 ! TS5 k(f) C3H6 + O = CH3CHCH + OH 1.200E+11 0.700 8960.00 ! TS5 k(E) C3H6 + OH = aC3H5 + H2O 3.100E+06 2.000 -298.00 ! TS5 C3H6 + OH = CH3CCH2 + H2O 1.100E+06 2.000 1450.00 ! TS5 C3H6 + OH = CH3CHCH + H2O 2.100E+06 2.000 2780.00 ! TS5 C3H6 + HO2 = aC3H5 + H2O2 9.600E+03 2.600 13910.00 ! TS5 C3H6 + CH3 = aC3H5 + CH4 2.200E+00 3.500 5675.00 ! TS5 C3H6 + CH3 = CH3CCH2 + CH4 8.400E-01 3.500 11660.00 ! TS5 C3H6 + CH3 = CH3CHCH + CH4 1.350E+00 3.500 12850.00 ! TS5 C3H6 + C2H3 = C4H6 + CH3 7.230E+11 0.000 5000.00 ! TS5 ! Reactions of n-propyl (nC3H7) nC3H7+H(+M) = C3H8(+M) 3.60E+13 0.00 0.0 ! TS3 600 cm-1 LOW / 3.01E+48 -9.32 5833.6 / TROE / 0.498 1314.0 1314.0 50000.0 / H2/2/ H2O/6/ CH4/2/ CO/1.5/ CO2/2/ C2H6/3/ AR/0.7/ !nC3H7+H = C2H5+CH3 3.40E+18 -1.33 5386.0 ! TS3 0.1 atm nC3H7+H = C2H5+CH3 3.70E+24 -2.92 12505.0 ! TS3 1 atm !nC3H7+H = C2H5+CH3 3.10E+27 -3.59 19059.0 ! TS3 10 atm ! nC3H7+H = C3H6+H2 1.80E+12 0.00 0.0 ! TS3 nC3H7+O = C2H5+CH2O 9.60E+13 0.00 0.0 ! TS3 ka+kb nC3H7+OH = C3H6+H2O 2.40E+13 0.00 0.0 ! TS3 nC3H7+O2 = C3H6+HO2 9.00E+10 0.00 0.0 ! TS3 nC3H7+HO2 = C2H5+OH+CH2O 2.40E+13 0.00 0.0 ! TS3 nC3H7+HCO = C3H8+CO 6.00E+13 0.00 0.0 ! TS3 nC3H7+CH3 = CH4+C3H6 1.10E+13 0.00 0.0 ! TS3 ! ! Reactions of i-propyl ! iC3H7+H(+M) = C3H8(+M) 2.40E+13 0.00 0.0 ! TS3 600 cm-1 LOW / 1.70E+58 -12.08 11263.7 / TROE / 0.649 1213.1 1213.1 13369.7 / H2/2/ H2O/6/ CH4/2/ CO/1.5/ CO2/2/ C2H6/3/ AR/0.7/ !iC3H7+H = CH3+C2H5 5.90E+23 -2.81 10009.0 ! TS3 0.1 atm iC3H7+H = CH3+C2H5 1.40E+28 -3.94 15916.0 ! TS3 1 atm !iC3H7+H = CH3+C2H5 4.00E+24 -2.83 17542.0 ! TS3 10 atm ! iC3H7+H = C3H6+H2 3.20E+12 0.00 0.0 ! TS3 iC3H7+O = CH3CHO+CH3 9.60E+13 0.00 0.0 ! TS3 ka+kb iC3H7+OH = C3H6+H2O 2.40E+13 0.00 0.0 ! TS3 iC3H7+O2 = C3H6+HO2 1.30E+11 0.00 0.0 ! TS3 iC3H7+HO2 = CH3CHO+CH3+OH 2.40E+13 0.00 0.0 ! TS3 iC3H7+HCO = C3H8+CO 1.20E+14 0.00 0.0 ! TS3 iC3H7+CH3 = CH4 + C3H6 2.20E+14 -0.68 0.0 ! TS3 ! ! Reactions of propane ! CH3+C2H5(+M) = C3H8(+M) 4.90E+14 -0.50 0.0 ! TS3 TS1 500cm-1 LOW / 6.80E+61 -13.42 6000.0 / TROE / 1.000 1000.0 1433.9 5328.8 / H2/2/ H2O/6/ CH4/2/ CO/1.5/ CO2/2/ C2H6/3/ AR/0.7/ C3H8+H = H2+nC3H7 1.30E+06 2.54 6756.0 ! TS3 C3H8+H = H2+iC3H7 1.30E+06 2.40 4471.0 ! TS3 C3H8+O = nC3H7+OH 1.90E+05 2.68 3716.0 ! TS3 C3H8+O = iC3H7+OH 4.76E+04 2.71 2106.0 ! TS3 C3H8+OH = nC3H7+H2O 1.40E+03 2.66 527.0 ! TS3 C3H8+OH = iC3H7+H2O 2.70E+04 2.39 393.0 ! TS3 C3H8+O2 = nC3H7+HO2 4.00E+13 0.00 50930.0 ! TS3 C3H8+O2 = iC3H7+HO2 4.00E+13 0.00 47590.0 ! TS3 C3H8+HO2 = nC3H7+H2O2 4.76E+04 2.55 16490.0 ! TS3 C3H8+HO2 = iC3H7+H2O2 9.64E+03 2.60 13910.0 ! TS3 C3H8+CH3 = CH4+nC3H7 9.03E-01 3.65 7153.0 ! TS3 C3H8+CH3 = CH4+iC3H7 1.51E+00 3.46 5480.0 ! TS3 ! Reactions of C4H C4H + H (+M) = C4H2 (+M) 1.000E+17 -1.000 0.00 ! LOW / 3.750E+33 -4.800 1900.00/ TROE/ 0.6464 132.00 1315.00 5566.00 / H2/2.0/ H2O/6.0/ CH4/2.0/ CO/1.5/ CO2/2.0/ C2H6/3.0/ AR/0.7/ C2H2/3.00/ C2H4/3.00/ C4H + O = C2H + C2O 5.000E+13 0.000 0.00 ! = C2H + O C4H + O2 = HCCO + C2O 5.000E+13 0.000 1500.00 ! = C2H + O2 C4H + H2 = H + C4H2 4.900E+05 2.500 560.00 ! = C2H + H2 ! Reactions of C4H2 C4H2 + H (+M) = n-C4H3 (+M) 1.550E+10 0.923 954.00 ! RRKM LOW /4.700E+47 -9.369 4090.00 / TROE /0.202 447.0 1162.0 2635.0 / H2/2.0/ H2O/6.0/ CH4/2.0/ CO/1.5/ CO2/2.0/ C2H6/3.0/ C2H2/3.00/ C2H4/3.00/ C4H2 + H (+M) = i-C4H3 (+M) 2.200E+10 0.940 164.00 ! RRKM LOW /1.100E+52 -10.251 4600.00 / TROE / 1.0 515. 515. 2550. / H2/2.0/ H2O/6.0/ CH4/2.0/ CO/1.5/ CO2/2.0/ C2H6/3.0/ C2H2/3.00/ C2H4/3.00/ C4H2 + O = C3H2 + CO 2.700E+13 0.000 1720.00 ! 84WAR C4H2 + OH = H2C4O + H 6.600E+12 0.000 -410.00 ! 84PER C4H2 + OH = C4H + H2O 3.370E+07 2.000 14000.00 ! = C2H2 + OH ! Reactions of H2C4O H2C4O + H = C2H2 + HCCO 5.000E+13 0.000 3000.00 ! Miller-Melius H2C4O + OH = CH2CO + HCCO 1.000E+07 2.000 2000.00 ! Miller-Melius H2C4O + O = CH2CO + C2O 2.000E+07 1.900 200.00 ! Estimated ! Reactions of C4H3 and C4H4 !n-C4H3 = i-C4H3 1.016E+56 -14.208 51818.78 ! RRKM 20 Torr !n-C4H3 = i-C4H3 6.494E+52 -13.015 51552.62 ! RRKM 76 Torr !n-C4H3 = i-C4H3 7.316E+47 -11.287 50694.04 ! RRKM 380 Torr n-C4H3 = i-C4H3 2.455E+45 -10.453 50149.54 ! RRKM 760 Torr !n-C4H3 = i-C4H3 5.523E+42 -9.573 49510.45 ! RRKM 1520 Torr !n-C4H3 = i-C4H3 1.338E+41 -9.042 49097.76 ! RRKM 2280 Torr !n-C4H3 = i-C4H3 9.055E+39 -8.659 48790.03 ! RRKM 3040 Torr !n-C4H3 = i-C4H3 1.091E+39 -8.360 48543.31 ! RRKM 3800 Torr !n-C4H3 = i-C4H3 1.899E+38 -8.113 48336.31 ! RRKM 4560 Torr !n-C4H3 = i-C4H3 4.322E+37 -7.905 48159.18 ! RRKM 5320 Torr !n-C4H3 = i-C4H3 1.190E+37 -7.724 48003.40 ! RRKM 6080 Torr !n-C4H3 = i-C4H3 1.372E+36 -7.421 47739.80 ! RRKM 7600 Torr n-C4H3 + H (+M) = C4H4 (+M) 1.000E+14 0.000 0.00 ! Estimated, RRKM LOW /1.700E+48 -9.437 7480.00 / TROE /0.62 6590. 2752./ H2/2.0/ H2O/6.0/ CH4/2.0/ CO/1.5/ CO2/2.0/ C2H6/3.0/ C2H2/3.0/ C2H4/3.0/ ! !n-C4H3+H = i-C4H3+H 4.543E+13 0.139 2988.83 ! RRKM 20 Torr !n-C4H3+H = i-C4H3+H 1.406E+14 0.004 3404.80 ! RRKM 76 Torr !n-C4H3+H = i-C4H3+H 2.114E+16 -0.596 5238.25 ! RRKM 380 Torr n-C4H3+H = i-C4H3+H 9.301E+17 -1.047 6672.68 ! RRKM 760 Torr !n-C4H3+H = i-C4H3+H 1.213E+20 -1.625 8589.81 ! RRKM 1520 Torr !n-C4H3+H = i-C4H3+H 2.217E+21 -1.968 9806.54 ! RRKM 2280 Torr !n-C4H3+H = i-C4H3+H 0.266E+23 -2.260 10827.79 ! RRKM 3040 Torr !n-C4H3+H = i-C4H3+H 1.540E+23 -2.467 11589.67 ! RRKM 3800 Torr !n-C4H3+H = i-C4H3+H 5.791E+23 -2.621 12193.04 ! RRKM 4560 Torr !n-C4H3+H = i-C4H3+H 1.711E+24 -2.747 12703.18 ! RRKM 5320 Torr !n-C4H3+H = i-C4H3+H 5.016E+24 -2.871 13208.17 ! RRKM 6080 Torr !n-C4H3+H = i-C4H3+H 2.599E+25 -3.062 13995.37 ! RRKM 7600 Torr ! !n-C4H3+H = C2H2+H2CC 8.316E+20 -2.127 3097.74 ! RRKM 20 Torr !n-C4H3+H = C2H2+H2CC 7.842E+21 -2.395 3928.33 ! RRKM 76 Torr !n-C4H3+H = C2H2+H2CC 8.063E+24 -3.221 6577.33 ! RRKM 380 Torr n-C4H3+H = C2H2+H2CC 7.450E+26 -3.757 8405.16 ! RRKM 760 Torr !n-C4H3+H = C2H2+H2CC 1.433E+29 -4.375 10649.88 ! RRKM 1520 Torr !n-C4H3+H = C2H2+H2CC 2.141E+30 -4.688 11939.79 ! RRKM 2280 Torr !n-C4H3+H = C2H2+H2CC 1.344E+31 -4.899 12873.82 ! RRKM 3040 Torr !n-C4H3+H = C2H2+H2CC 5.504E+31 -5.059 13617.72 ! RRKM 3800 Torr !n-C4H3+H = C2H2+H2CC 1.239E+32 -5.149 14131.93 ! RRKM 4560 Torr !n-C4H3+H = C2H2+H2CC 2.339E+32 -5.218 14568.43 ! RRKM 5320 Torr !n-C4H3+H = C2H2+H2CC 3.168E+32 -5.247 14884.21 ! RRKM 6080 Torr !n-C4H3+H = C2H2+H2CC 8.825E+32 -5.360 15562.11 ! RRKM 7600 Torr !i-C4H3+H = C2H2+H2CC 2.621E+25 -3.322 7094.20 ! RRKM 20 Torr !i-C4H3+H = C2H2+H2CC 1.492E+27 -3.803 8639.05 ! RRKM 76 Torr !i-C4H3+H = C2H2+H2CC 2.220E+31 -4.938 12578.19 ! RRKM 380 Torr i-C4H3+H = C2H2+H2CC 2.595E+33 -5.491 14785.66 ! RRKM 760 Torr !i-C4H3+H = C2H2+H2CC 1.343E+35 -5.939 16938.64 ! RRKM 1520 Torr !i-C4H3+H = C2H2+H2CC 5.812E+35 -6.096 18021.31 ! RRKM 2280 Torr !i-C4H3+H = C2H2+H2CC 9.417E+35 -6.138 18668.21 ! RRKM 3040 Torr !i-C4H3+H = C2H2+H2CC 1.707E+36 -6.197 19247.76 ! RRKM 3800 Torr !i-C4H3+H = C2H2+H2CC 1.842E+36 -6.195 19607.40 ! RRKM 4560 Torr !i-C4H3+H = C2H2+H2CC 1.892E+36 -6.188 19914.10 ! RRKM 5320 Torr !i-C4H3+H = C2H2+H2CC 1.552E+36 -6.156 20109.15 ! RRKM 6080 Torr !i-C4H3+H = C2H2+H2CC 9.586E+35 -6.083 20410.18 ! RRKM 7600 Torr i-C4H3 + H (+M) = C4H4 (+M) 1.000E+14 0.000 0.00 ! Estimated, RRKM LOW /1.100E+53 -10.703 9100.00 / TROE /0.40 5600. 1434. 8728. / H2/2.0/ H2O/6.0/ CH4/2.0/ CO/1.5/ CO2/2.0/ C2H6/3.0/ C2H2/3.00/ C2H4/3.00/ n-C4H3 + H = C4H2 + H2 3.000E+13 0.000 0.00 ! 0.5*C2H3 + H i-C4H3 + H = C4H2 + H2 6.000E+13 0.000 0.00 ! C2H3 + H n-C4H3 + OH = C4H2 + H2O 2.000E+12 0.000 0.00 ! i-C4H3 + OH = C4H2 + H2O 4.000E+12 0.000 0.00 ! i-C4H3 + O2 = HCCO + CH2CO 7.860E+16 -1.800 0.00 ! Gutman ! Reactions of C4H4 C4H4 + H = n-C4H5 1.300E+51 -11.92 16500.00 ! 760 Torr C4H4 + H = i-C4H5 4.900E+51 -11.92 17700.00 ! 760 Torr C4H4 + H = n-C4H3 + H2 6.650E+05 2.530 12240.00 ! =(C2H4 + H)/2 C4H4 + H = i-C4H3 + H2 3.330E+05 2.530 9240.00 ! -3kcal/mol, /4 C4H4 + O = C3H3 + HCO 1.500E+13 0.000 1808.00 ! NIST C4H4 + OH = n-C4H3 + H2O 3.100E+07 2.000 3430.00 ! = C4H6 + OH C4H4 + OH = i-C4H3 + H2O 1.550E+07 2.000 430.00 ! -3kcal/mol, /2 C4H4 + CH3 = n-C4H3 + CH4 3.980E+11 0.000 4972.00 ! 85SCH/CLA C4H4 + CH3 = i-C4H3 + CH4 3.980E+11 0.000 4972.00 ! 85SCH/CLA C4H4 + C2H = n-C4H3 + C2H2 3.900E+13 0.000 0.00 ! 80TAN/GAR C4H4 + C2H = i-C4H3 + C2H2 3.900E+13 0.000 0.00 ! 80TAN/GAR ! ! Reactions of C4H5 and 1,3-C4H6 ! n-C4H5 = i-C4H5 1.5E+67 -16.89 59100. ! 760 t n-C4H5 + H = i-C4H5 + H 3.1E+26 -3.35 17423. ! RRKM 760 t C4H6 = i-C4H5 + H 5.7E+36 -6.27 112353. ! RRKM 760 t C4H6 = n-C4H5 + H 5.3E+44 -8.62 123608. ! RRKM 760 t n-C4H5 + H = C4H4 + H2 1.5E+13 0.00 0. i-C4H5 + H = C4H4 + H2 3.0E+13 0.00 0. n-C4H5 + OH = C4H4 + H2O 2.0E+12 0.00 0. i-C4H5 + OH = C4H4 + H2O 4.0E+12 0.00 0. n-C4H5 + HCO = C4H6 + CO 5.00E+12 0.0 0. ! Estimated i-C4H5 + HCO = C4H6 + CO 5.00E+12 0.0 0. ! Estimated n-C4H5 + HO2 = C2H3 + CH2CO + OH 6.60E+12 0.0 0. ! Estimated i-C4H5 + HO2 = C2H3 + CH2CO + OH 6.60E+12 0.0 0. ! Estimated n-C4H5 + H2O2 = C4H6 + HO2 1.210E+10 0.000 -596.00! estC2h3 i-C4H5 + H2O2 = C4H6 + HO2 1.210E+10 0.000 -596.00! estC2h3 ! C4H6 + H = n-C4H5 + H2 1.33E+06 2.53 12240.0 ! = C2H4 + H C4H6 + H = i-C4H5 + H2 6.65E+05 2.53 9240.0 ! -3kcal/mol,/2 C4H6 + H = pC3H4 + CH3 7.00E+12 0.0 8000.0 ! Est. C4H6 + O = n-C4H5+OH 0.750E+07 1.900 3740 ! =C2h4+O C4H6 + O = i-C4H5+OH 0.750E+07 1.900 3740 ! =C2h4+O C4H6 + OH = n-C4H5 + H2O 6.20E+06 2.0 3430.0 ! refit to Liu C4H6 + OH = i-C4H5 + H2O 3.10E+06 2.0 430.0 ! -3kcal/mol C4H6 + CH3 = i-C4H5 + CH4 7.00E+13 0.0 15500.0 ! est C4H6 + CH3 = n-C4H5 + CH4 7.00E+13 0.0 18500.0 ! est C4H6 + HCO = C4H7 + CO 3.50E+11 0.0 4000.0 ! est ! ! Reactions of 1,2-C4H6 ! C4H612 + H = C4H6 + H 2.00E+13 0.0 4000.0 ! Estimated C4H612 + H = i-C4H5 + H2 1.70E+05 2.5 2490.0 ! = C3H6+H TS5 C4H612 + H = aC3H4 + CH3 2.00E+13 0.0 2000.0 ! Estimated C4H612 + H = pC3H4 + CH3 2.00E+13 0.0 2000.0 ! Estimated C4H612 + O = CH2CO + C2H4 1.20E+08 1.65 327.0 ! C3H6+O TS5 C4H612 + O = i-C4H5 + OH 1.80E+11 0.70 5880.0 ! C3H6+O TS5 C4H612 + OH = i-C4H5 + H2O 3.10E+06 2.00 -298.0 ! C3H6+OH C4H612 + CH3 = i-C4H5 + CH4 7.00E+13 0.0 18500.0 ! nist C4H612 = C4H6 3.00E+13 0.0 65000.0 ! Hid/Hig96 ! ! Reactions of 1-buten-3-yl ! !C4H7 = C4H6+H 1.55E+56 -13.46 50860.0 ! HW 0.1 atm & C4H7 = C4H6+H 2.28E+52 -12.01 51230.0 ! HW 1 atm !C4H7 = C4H6+H 2.25E+44 -9.39 49150.0 ! HW 10 atm ! C4H7+H(+M) = C4H81(+M) 3.60E+13 0.00 0.0 ! =(nC3H7+H) TS3 600 cm- 1 LOW / 3.01E+48 -9.32 5833.6 / TROE / 0.498 1314.0 1314.0 50000.0 / H2/2/ H2O/6/ CH4/2/ CO/1.5/ CO2/2/ C2H6/3/ AR/0.7/ C4H7+H = CH3+aC3H5 2.00E+21 -2.00 11000.0 ! Estimated C4H7+H = C4H6+H2 1.80E+12 0.00 0.0 ! =(nC3H7+H) TS3 C4H7+O2 = C4H6+HO2 1.00E+11 0.00 0.0 ! Estimated C4H7+HO2 = CH2O+OH+aC3H5 2.40E+13 0.00 0.0 ! =(nC3H7+HO2) TS3 C4H7+HCO = C4H81+CO 6.00E+13 0.00 0.0 ! =(nC3H7+HCO) TS3 C4H7+CH3 = C4H6+CH4 1.10E+13 0.00 0.0 ! =(nC3H7+CH3) ! ! Reactions of 1-butene ! C2H3+C2H5(+M) = C4H81(+M) 1.50E+13 0.00 0.0 ! TS1 450cm-1 LOW / 1.55E+56 -11.79 8984.5 / TROE / 0.198 2277.9 60000.0 5723.2 / H2/2/ H2O/6/ CH4/2/ CO/1.5/ CO2/2/ C2H6/3/ AR/0.7/ !C2H3+C2H5 = aC3H5+CH3 8.00E+25 -3.46 11775.0 ! TS1 0.1 atm C2H3+C2H5 = aC3H5+CH3 3.90E+32 -5.22 19747.0 ! TS1 1 atm !C2H3+C2H5 = aC3H5+CH3 3.90E+29 -4.24 22311.0 ! TS1 10 atm ! ! kinf: -0.5 T power = CH3+C2H5, kinf(300K) = TS1 recommendation ! ko: scaled such that Pr(C2H5+C2H5) = Pr(CH3+C2H5) at (T,P), 500 cm-1 ! Fc: assumed equal to Fc(CH3+C2H5) ! !C4H81+H = C2H4+C2H5 8.80E+16 -1.05 6461.0 ! =(C3H6+H) TS5 0.1 atm C4H81+H = C2H4+C2H5 1.60E+22 -2.39 11180.0 ! =(C3H6+H) TS5 1 atm*2 !C4H81+H = C2H4+C2H5 3.30E+24 -3.04 15610.0 ! =(C3H6+H) TS5 10 atm C4H81+H = C3H6+CH3 3.20E+22 -2.39 11180.0 ! =(C4H81+H)*2 ! C4H81+H = C4H7+H2 6.50E+05 2.54 6756.0 ! =(C3H8+H)/2 TS5 k(a) C4H81+O = nC3H7+HCO 3.30E+08 1.45 -402.0 ! Refit to Fontijn kadd C4H81+O = C4H7+OH 1.50E+13 0.00 5760.0 ! Fontijn duplicate C4H81+O = C4H7+OH 2.60E+13 0.00 4470.0 ! Fontijn duplicate C4H81+OH = C4H7+H2O 7.00E+02 2.66 527.0 ! =(C3H8+OH)/2 TS5 C4H81+O2 = C4H7+HO2 2.00E+13 0.00 50930.0 ! =(C3H8+O2)/2 TS5 !C4H81+HO2 = C4H7+H2O2 2.40E+04 2.55 16490.0 ! =(C3H8+HO2)/2 TS3 C4H81+HO2 = C4H7+H2O2 1.50E+11 0.00 14900.0 ! Walker 77 (/2) C4H81+CH3 = C4H7+CH4 4.50E-01 3.65 7153.0 ! =(C3H8+CH3)/2 TS5 k(c) ! ! Reactions up to benzene formation and oxidation ! C4H2 + C2H = C6H2 + H 9.60E+13 0.0 0.0 ! = C2H2 + C2H C4H2 + C2H = C6H3 4.50E+37 -7.68 7100.0 ! RRKM, 760 t n-C4H3 + C2H2 = l-C6H4 + H 2.5E+14 -0.56 10600. ! 760 t n-C4H3 + C2H2 = A1- 9.6E+70 -17.77 31300. ! 760 t n-C4H3 + C2H2 = c-C6H4 + H 6.9E+46 -10.01 30100. ! 760 t C4H4 + C2H = l-C6H4 + H 1.20E+13 0.0 0.0 ! = C2H+C2H4 n-C4H5 + C2H2 = A1 + H 1.6E+16 -1.33 5400. ! 760 t n-C4H5 + C2H3 = A1 + H2 1.84E+13 0.0 7070. ! NIST C4H6 + C2H3 = A1 + H2 +H 2.23E+7 1.31 1369. ! NIST ! ! Reactions of C6H2 ! C6H2 + H = C6H3 1.10E+30 -4.92 10800.0 ! RRKM, 760 t ! ! Reactions of C6H3 and C6H4 ! C6H3 + H = C4H2 + C2H2 2.80E+23 -2.55 10780.0 ! RRKM, 760 t C6H3 + H = l-C6H4 3.40E+43 -9.01 12120.0 ! RRKM, 760 t C6H3 + H = C6H2 + H2 3.00E+13 0.00 0.0 ! C2H3+H C6H3 + OH = C6H2 + H2O 4.00E+12 0.00 0.0 C6H3+O2 => CO+C3H2+HCCO 5.00E+11 0.00 0.0 ! Estimated l-C6H4 + H = A1- 1.7E+78 -19.72 31400. ! 760 t l-C6H4 + H = c-C6H4+ H 1.4E+54 -11.70 34500. ! 760 t l-C6H4 + H = C6H3 + H2 1.33E+06 2.53 9240.0 ! = C4H4+H l-C6H4 + OH = C6H3 + H2O 3.10E+06 2.0 430.0 ! see notes c-C6H4 + H = A1- 2.4E+60 -13.66 29500. ! 760 t ! ! Reactions of benzene and phenyl ! A1 + H = A1- + H2 2.50E+14 0.0 16000. ! Kiefer A1 + OH = A1- + H2O 1.60E+08 1.42 1450.0 ! CEC ! A1- + H (+M) = A1 (+M) 1.0E+14 0.00 0. LOW/ 6.6E+75 -16.30 7000. / TROE / 1.0 0.1 584.9 6113. / H2/2.0/ H2O/6.0/ CH4/2.0/ CO/1.5/ CO2/2.0/ C2H6/3.0/ ! ! Benzene oxidation ! A1 + O = C6H5O + H 2.20E+13 0.0 4530.0 ! CEC A1 + OH = C6H5OH + H 1.30E+13 0.0 10600.0 ! CEC A1- + O2 = C6H5O + O 2.60E+13 0.00 6120.0 ! (Frank et al.) ! C6H5O = CO + C5H5 7.41E+11 0.0 43900.0 ! Frank et al. C6H5O + H = CO + C5H6 3.00E+13 0.0 0.0 ! Est. C6H5O + O = HCO + 2C2H2 + CO 3.00E+13 0.0 0.0 ! Est. C6H5O + H (+M) = C6H5OH (+M) 2.50E+14 0.0 0.0 ! (He et al.) LOW/1.00E+94 -21.84 13880.0/ ! (HW, RRKM needs exam) TROE/0.043 304.2 60000. 5896.4/ H2/2./ H2O/6./ CH4/2./ CO/1.5/ CO2/2./ ! C6H5OH + H = C6H5O + H2 1.15E+14 0.0 12400.0 ! LIN C6H5OH + O = C6H5O + OH 2.80E+13 0.0 7352.0 ! Brezinski C6H5OH + OH = C6H5O + H2O 6.00E+12 0.0 0.0 ! LIN ! C5H5 + H (+M)= C5H6 (+M) 1.00E+14 0.0 0.0 ! (est. EBG) LOW/4.4E+80 -18.28 12994.0/ ! (HW, RRKM) TROE/0.068 400.7 4135.8 5501.9/ H2/2./ H2O/6./ CH4/2./ CO/1.5/ CO2/2./ C5H5 + O = n-C4H5 + CO 1.00E+14 0.0 0.0 ! Brezinsky C5H5 + OH = C5H4OH + H 5.00E+12 0.0 0.0 ! Est. C5H5 + HO2 = C5H5O + OH 3.00E+13 0.0 0.0 ! Brezinsky ! C5H6 + H = C5H5 + H2 2.20E+08 1.77 3000.0 ! Brezinsky C5H6 + O = C5H5 + OH 1.80E+13 0.0 3080.0 ! Brezinsky C5H6 + OH = C5H5 + H2O 3.43E+09 1.18 -447.0 ! Brezinsky ! C5H5O = n-C4H5 + CO 2.50E+11 0.0 43900.0 ! Brezinsky C5H5O + H = CH2O + 2C2H2 3.00E+13 0.0 0.0 ! Est. C5H5O + O = CO2 + n-C4H5 3.00E+13 0.0 0.0 ! Est. ! C5H4OH = C5H4O + H 2.10E+13 0.0 48000.0 ! Brezinsky C5H4OH + H = CH2O + 2C2H2 3.00E+13 0.0 0.0 ! Est. C5H4OH + O = CO2 + n-C4H5 3.00E+13 0.0 0.0 ! Est. ! C5H4O = CO + C2H2 + C2H2 1.00E+15 0.0 78000.0 ! Brezinsky C5H4O + O = CO2 + 2C2H2 3.00E+13 0.0 0.0 ! Est END !****************** ! ! PW Pitz and Westbrook ! HW Wang RRKM calcl ! CEC EC compilation ! TS1 Tsang, methane compilation ! TS3 Tsang, propane compilation ! TS4 Tsang, isobutane compilation ! TS5 Tsang, propene compilation ! TW Tsang, W. and Walker, J. A. J. Phys. Chem. 96:8378-8384 (1992). ! CW Cohen, N. and Westberg, K. R., Int. J. Chem. Kinet. 18:99 (1986) ! C Cohen, N. Int. J. Chem. Kinet. 23:397-417 (1991) ! 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