! ! Reference: ! ! Z. Qin, V. V. Lissianski, H. Yang, W. C. Gardiner, Jr., S. G. Davis ! and H. Wang, “Combustion Chemistry Of Propane: A Case Study of Detailed ! Reaction Mechanism Optimization,” Proceedings of the Combustion Institute, ! Volume 28, 2000. p. 1663–1669. ! ELEMENTS C H O 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 C2H3 C2H4 C2H5 C2H6 HCCO CH2CO HCCOH ! AR N2 CH2CHO C3H2 C3H3 pC3H4 aC3H4 cC3H4 C4H2 H2C4O n-C4H3 i-C4H3 C4H4 n-C4H5 i-C4H5 C4H6 C4H612 C4H81 C4H7 C6H2 C6H3 l-C6H4 c-C6H4 A1 A1- C6H5O C6H5OH C5H6 C5H5 C5H5O C5H4OH C5H4O C3H8 nC3H7 iC3H7 C3H6 aC3H5 CH3CCH2 CH3CHO C2H3CHO END ! GRI-Mech Version 3.0 7/30/99 CHEMKIN-II format (C < 3) and ( Qin&Scott C3 & Scott C4-C6 ) REACTIONS 2O+M<=>O2+M 1.200E+17 -1.000 .00 H2/ 2.40/ H2O/15.40/ CH4/ 2.00/ CO/ 1.75/ CO2/ 3.60/ C2H6/ 3.00/ AR/ .83/ C2H4/3.0/ pC3H4/4.0/ C3H6/4.0/ C3H8/4.0/ O+H+M<=>OH+M 5.000E+17 -1.000 .00 H2/2.00/ H2O/6.00/ CH4/2.00/ CO/1.50/ CO2/2.00/ C2H6/3.00/ AR/ .70/ C2H4/3.0/ pC3H4/4.0/ C3H6/4.0/ C3H8/4.0/ O+H2<=>H+OH 3.870E+04 2.700 6260.00 O+HO2<=>OH+O2 2.000E+13 .000 .00 O+H2O2<=>OH+HO2 9.630E+06 2.000 4000.00 O+CH<=>H+CO 5.700E+13 .000 .00 O+CH2<=>H+HCO 8.000E+13 .000 .00 O+CH2*<=>H2+CO 1.500E+13 .000 .00 O+CH2*<=>H+HCO 1.500E+13 .000 .00 O+CH3<=>H+CH2O 5.060E+13 .000 .00 O+CH4<=>OH+CH3 1.020E+09 1.500 8600.00 O+CO(+M)<=>CO2(+M) 1.800E+10 .000 2385.00 LOW/ 6.020E+14 .000 3000.00/ H2/2.00/ O2/6.00/ H2O/6.00/ CH4/2.00/ CO/1.50/ CO2/3.50/ C2H6/3.00/ AR/ .50/ C2H4/3.0/ pC3H4/4.0/ C3H6/4.0/ C3H8/4.0/ O+HCO<=>OH+CO 3.000E+13 .000 .00 O+HCO<=>H+CO2 3.000E+13 .000 .00 O+CH2O<=>OH+HCO 3.900E+13 .000 3540.00 O+CH2OH<=>OH+CH2O 1.000E+13 .000 .00 O+CH3O<=>OH+CH2O 1.000E+13 .000 .00 O+CH3OH<=>OH+CH2OH 3.880E+05 2.500 3100.00 O+CH3OH<=>OH+CH3O 1.300E+05 2.500 5000.00 O+C2H<=>CH+CO 5.000E+13 .000 .00 O+C2H2<=>H+HCCO 1.350E+07 2.000 1900.00 O+C2H2<=>OH+C2H 4.600E+19 -1.410 28950.00 O+C2H2<=>CO+CH2 6.940E+06 2.000 1900.00 O+C2H3<=>H+CH2CO 3.000E+13 .000 .00 O+C2H4<=>CH3+HCO 2.500E+07 1.830 220.00 ! k_opt=2*ko O+C2H5<=>CH3+CH2O 2.240E+13 .000 .00 O+C2H6<=>OH+C2H5 8.980E+07 1.920 5690.00 O+HCCO<=>H+2CO 1.000E+14 .000 .00 O+CH2CO<=>OH+HCCO 1.000E+13 .000 8000.00 O+CH2CO<=>CH2+CO2 1.750E+12 .000 1350.00 O2+CO<=>O+CO2 2.500E+12 .000 47800.00 O2+CH2O<=>HO2+HCO 1.000E+14 .000 40000.00 H+O2+M<=>HO2+M 2.800E+18 -.860 .00 O2/ .00/ H2O/ .00/ CO/ .75/ CO2/1.50/ C2H6/1.50/ N2/ .00/ AR/ .00/ C2H4/3.0/ pC3H4/4.0/ C3H6/4.0/ C3H8/4.0/ H+2O2<=>HO2+O2 2.080E+19 -1.240 .00 H+O2+H2O<=>HO2+H2O 11.26E+18 -.760 .00 H+O2+N2<=>HO2+N2 2.600E+19 -1.240 .00 H+O2+AR<=>HO2+AR 7.000E+17 -.800 .00 H+O2<=>O+OH 2.650E+16 -.6707 17041.00 2H+M<=>H2+M 1.000E+18 -1.000 .00 H2/ .00/ H2O/ .00/ CH4/2.00/ CO2/ .00/ C2H6/3.00/ AR/ .63/ C2H4/3.0/ pC3H4/4.0/ C3H6/4.0/ C3H8/4.0/ 2H+H2<=>2H2 9.000E+16 -.600 .00 2H+H2O<=>H2+H2O 6.000E+19 -1.250 .00 2H+CO2<=>H2+CO2 5.500E+20 -2.000 .00 H+OH+M<=>H2O+M 2.200E+22 -2.000 .00 H2/ .73/ H2O/3.65/ CH4/2.00/ C2H6/3.00/ AR/ .38/ C2H4/3.0/ pC3H4/4.0/ C3H6/4.0/ C3H8/4.0/ H+HO2<=>O+H2O 3.970E+12 .000 671.00 H+HO2<=>O2+H2 7.750E+13 .000 1068.00 ! k_opt=1.73*ko H+HO2<=>2OH 0.420E+14 .000 635.00 ! k_opt=0.5*ko H+H2O2<=>HO2+H2 1.210E+07 2.000 5200.00 H+H2O2<=>OH+H2O 1.000E+13 .000 3600.00 H+CH<=>C+H2 1.650E+14 .000 .00 H+CH2(+M)<=>CH3(+M) 6.000E+14 .000 .00 LOW / 1.040E+26 -2.760 1600.00/ TROE/ .5620 91.00 5836.00 8552.00/ H2/2.00/ H2O/6.00/ CH4/2.00/ CO/1.50/ CO2/2.00/ C2H6/3.00/ AR/ .70/ C2H4/3.0/ pC3H4/4.0/ C3H6/4.0/ C3H8/4.0/ H+CH2*<=>CH+H2 3.000E+13 .000 .00 H+CH3(+M)<=>CH4(+M) 13.90E+15 -.534 536.00 LOW / 2.620E+33 -4.760 2440.00/ TROE/ .7830 74.00 2941.00 6964.00 / H2/2.00/ H2O/6.00/ CH4/3.00/ CO/1.50/ CO2/2.00/ C2H6/3.00/ AR/ .70/ C2H4/3.0/ pC3H4/4.0/ C3H6/4.0/ C3H8/4.0/ H+CH4<=>CH3+H2 6.600E+08 1.620 10840.00 H+HCO(+M)<=>CH2O(+M) 1.090E+12 .480 -260.00 LOW / 2.470E+24 -2.570 425.00/ TROE/ .7824 271.00 2755.00 6570.00 / H2/2.00/ H2O/6.00/ CH4/2.00/ CO/1.50/ CO2/2.00/ C2H6/3.00/ AR/ .70/ C2H4/3.0/ pC3H4/4.0/ C3H6/4.0/ C3H8/4.0/ H+HCO<=>H2+CO 7.340E+13 .000 .00 H+CH2O(+M)<=>CH2OH(+M) 5.400E+11 .454 3600.00 LOW / 1.270E+32 -4.820 6530.00/ TROE/ .7187 103.00 1291.00 4160.00 / H2/2.00/ H2O/6.00/ CH4/2.00/ CO/1.50/ CO2/2.00/ C2H6/3.00/ C2H4/3.0/ pC3H4/4.0/ C3H6/4.0/ C3H8/4.0/ H+CH2O(+M)<=>CH3O(+M) 5.400E+11 .454 2600.00 LOW / 2.200E+30 -4.800 5560.00/ TROE/ .7580 94.00 1555.00 4200.00 / H2/2.00/ H2O/6.00/ CH4/2.00/ CO/1.50/ CO2/2.00/ C2H6/3.00/ C2H4/3.0/ pC3H4/4.0/ C3H6/4.0/ C3H8/4.0/ H+CH2O<=>HCO+H2 5.740E+07 1.900 2742.00 H+CH2OH(+M)<=>CH3OH(+M) 1.055E+12 .500 86.00 LOW / 4.360E+31 -4.650 5080.00/ TROE/ .600 100.00 90000.0 10000.0 / H2/2.00/ H2O/6.00/ CH4/2.00/ CO/1.50/ CO2/2.00/ C2H6/3.00/ C2H4/3.0/ pC3H4/4.0/ C3H6/4.0/ C3H8/4.0/ H+CH2OH<=>H2+CH2O 2.000E+13 .000 .00 H+CH2OH<=>OH+CH3 1.650E+11 .650 -284.00 H+CH2OH<=>CH2*+H2O 3.280E+13 -.090 610.00 H+CH3O(+M)<=>CH3OH(+M) 2.430E+12 .515 50.00 LOW / 4.660E+41 -7.440 14080.0/ TROE/ .700 100.00 90000.0 10000.00 / H2/2.00/ H2O/6.00/ CH4/2.00/ CO/1.50/ CO2/2.00/ C2H6/3.00/ C2H4/3.0/ pC3H4/4.0/ C3H6/4.0/ C3H8/4.0/ H+CH3O<=>H+CH2OH 4.150E+07 1.630 1924.00 H+CH3O<=>H2+CH2O 2.000E+13 .000 .00 H+CH3O<=>OH+CH3 1.500E+12 .500 -110.00 H+CH3O<=>CH2*+H2O 2.620E+14 -.230 1070.00 H+CH3OH<=>CH2OH+H2 1.700E+07 2.100 4870.00 H+CH3OH<=>CH3O+H2 4.200E+06 2.100 4870.00 H+C2H(+M)<=>C2H2(+M) 1.000E+17 -1.000 .00 LOW / 3.750E+33 -4.800 1900.00/ TROE/ .6464 132.00 1315.00 5566.00 / H2/2.00/ H2O/6.00/ CH4/2.00/ CO/1.50/ CO2/2.00/ C2H6/3.00/ AR/ .70/ C2H4/3.0/ pC3H4/4.0/ C3H6/4.0/ C3H8/4.0/ H+C2H2(+M)<=>C2H3(+M) 5.600E+12 .000 2400.00 LOW / 3.800E+40 -7.270 7220.00/ TROE/ .7507 98.50 1302.00 4167.00 / H2/2.00/ H2O/6.00/ CH4/2.00/ CO/1.50/ CO2/2.00/ C2H6/3.00/ AR/ .70/ C2H4/3.0/ pC3H4/4.0/ C3H6/4.0/ C3H8/4.0/ H+C2H3(+M)<=>C2H4(+M) 6.080E+12 .270 280.00 LOW / 1.400E+30 -3.860 3320.00/ TROE/ .7820 207.50 2663.00 6095.00 / H2/2.00/ H2O/6.00/ CH4/2.00/ CO/1.50/ CO2/2.00/ C2H6/3.00/ AR/ .70/ C2H4/3.0/ pC3H4/4.0/ C3H6/4.0/ C3H8/4.0/ H+C2H3<=>H2+C2H2 3.030E+13 .000 .00 ! k_opt=1.01*ko H+C2H4(+M)<=>C2H5(+M) 0.783E+12 .454 1820.00 ! k_opt=1.45*ko LOW / 0.600E+42 -7.620 6970.00/ TROE/ .9753 210.00 984.00 4374.00 / H2/2.00/ H2O/6.00/ CH4/2.00/ CO/1.50/ CO2/2.00/ C2H6/3.00/ AR/ .70/ C2H4/3.0/ pC3H4/4.0/ C3H6/4.0/ C3H8/4.0/ H+C2H4<=>C2H3+H2 1.325E+06 2.530 12240.00 H+C2H5(+M)<=>C2H6(+M) 5.210E+17 -.990 1580.00 LOW / 1.990E+41 -7.080 6685.00/ TROE/ .8422 125.00 2219.00 6882.00 / H2/2.00/ H2O/6.00/ CH4/2.00/ CO/1.50/ CO2/2.00/ C2H6/3.00/ AR/ .70/ C2H4/3.0/ pC3H4/4.0/ C3H6/4.0/ C3H8/4.0/ H+C2H5<=>H2+C2H4 2.000E+12 .000 .00 H+C2H6<=>C2H5+H2 1.150E+08 1.900 7530.00 H+HCCO<=>CH2*+CO 1.000E+14 .000 .00 H+CH2CO<=>HCCO+H2 5.000E+13 .000 8000.00 H+CH2CO<=>CH3+CO 1.130E+13 .000 3428.00 H+HCCOH<=>H+CH2CO 1.000E+13 .000 .00 H2+CO(+M)<=>CH2O(+M) 4.300E+07 1.500 79600.00 LOW / 5.070E+27 -3.420 84350.00/ TROE/ .9320 197.00 1540.00 10300.00 / H2/2.00/ H2O/6.00/ CH4/2.00/ CO/1.50/ CO2/2.00/ C2H6/3.00/ AR/ .70/ C2H4/3.0/ pC3H4/4.0/ C3H6/4.0/ C3H8/4.0/ OH+H2<=>H+H2O 2.160E+08 1.510 3430.00 2OH(+M)<=>H2O2(+M) 7.400E+13 -.370 .00 LOW / 2.300E+18 -.900 -1700.00/ TROE/ .7346 94.00 1756.00 5182.00 / H2/2.00/ H2O/6.00/ CH4/2.00/ CO/1.50/ CO2/2.00/ C2H6/3.00/ AR/ .70/ C2H4/3.0/ pC3H4/4.0/ C3H6/4.0/ C3H8/4.0/ 2OH<=>O+H2O 3.570E+04 2.400 -2110.00 OH+HO2<=>O2+H2O 1.450E+13 .000 -500.00 DUPLICATE OH+H2O2<=>HO2+H2O 2.000E+12 .000 427.00 DUPLICATE OH+H2O2<=>HO2+H2O 1.700E+18 .000 29410.00 DUPLICATE OH+C<=>H+CO 5.000E+13 .000 .00 OH+CH<=>H+HCO 3.000E+13 .000 .00 OH+CH2<=>H+CH2O 2.000E+13 .000 .00 OH+CH2<=>CH+H2O 1.130E+07 2.000 3000.00 OH+CH2*<=>H+CH2O 3.000E+13 .000 .00 OH+CH3(+M)<=>CH3OH(+M) 2.790E+18 -1.430 1330.00 LOW / 4.000E+36 -5.920 3140.00/ TROE/ .4120 195.0 5900.00 6394.00/ H2/2.00/ H2O/6.00/ CH4/2.00/ CO/1.50/ CO2/2.00/ C2H6/3.00/ C2H4/3.0/ pC3H4/4.0/ C3H6/4.0/ C3H8/4.0/ OH+CH3<=>CH2+H2O 5.600E+07 1.600 5420.00 OH+CH3<=>CH2*+H2O 6.440E+17 -1.340 1417.00 OH+CH4<=>CH3+H2O 1.000E+08 1.600 3120.00 OH+CO<=>H+CO2 4.760E+07 1.228 70.00 OH+HCO<=>H2O+CO 5.000E+13 .000 .00 OH+CH2O<=>HCO+H2O 3.430E+09 1.180 -447.00 OH+CH2OH<=>H2O+CH2O 5.000E+12 .000 .00 OH+CH3O<=>H2O+CH2O 5.000E+12 .000 .00 OH+CH3OH<=>CH2OH+H2O 1.440E+06 2.000 -840.00 OH+CH3OH<=>CH3O+H2O 6.300E+06 2.000 1500.00 OH+C2H<=>H+HCCO 2.000E+13 .000 .00 OH+C2H2<=>H+CH2CO 2.180E-04 4.500 -1000.00 OH+C2H2<=>H+HCCOH 5.040E+05 2.300 13500.00 OH+C2H2<=>C2H+H2O 3.370E+07 2.000 14000.00 OH+C2H2<=>CH3+CO 4.830E-04 4.000 -2000.00 OH+C2H3<=>H2O+C2H2 5.000E+12 .000 .00 OH+C2H4<=>C2H3+H2O 1.800E+06 2.000 2500.00 ! k_opt=0.5*ko OH+C2H6<=>C2H5+H2O 3.540E+06 2.120 870.00 OH+CH2CO<=>HCCO+H2O 7.500E+12 .000 2000.00 2HO2<=>O2+H2O2 1.300E+11 .000 -1630.00 DUPLICATE 2HO2<=>O2+H2O2 4.200E+14 .000 12000.00 DUPLICATE HO2+CH2<=>OH+CH2O 2.000E+13 .000 .00 HO2+CH3<=>O2+CH4 1.000E+12 .000 .00 HO2+CH3<=>OH+CH3O 2.870E+13 .000 .00 ! k_opt=0.76*ko HO2+CO<=>OH+CO2 1.500E+14 .000 23600.00 HO2+CH2O<=>HCO+H2O2 5.600E+06 2.000 12000.00 C+O2<=>O+CO 5.800E+13 .000 576.00 C+CH2<=>H+C2H 5.000E+13 .000 .00 C+CH3<=>H+C2H2 5.000E+13 .000 .00 CH+O2<=>O+HCO 6.710E+13 .000 .00 CH+H2<=>H+CH2 1.080E+14 .000 3110.00 CH+H2O<=>H+CH2O 5.710E+12 .000 -755.00 CH+CH2<=>H+C2H2 4.000E+13 .000 .00 CH+CH3<=>H+C2H3 3.000E+13 .000 .00 CH+CH4<=>H+C2H4 6.000E+13 .000 .00 CH+CO(+M)<=>HCCO(+M) 5.000E+13 .000 .00 LOW / 2.690E+28 -3.740 1936.00/ TROE/ .5757 237.00 1652.00 5069.00 / H2/2.00/ H2O/6.00/ CH4/2.00/ CO/1.50/ CO2/2.00/ C2H6/3.00/ AR/ .70/ C2H4/3.0/ pC3H4/4.0/ C3H6/4.0/ C3H8/4.0/ CH+CO2<=>HCO+CO 1.900E+14 .000 15792.00 CH+CH2O<=>H+CH2CO 9.460E+13 .000 -515.00 CH+HCCO<=>CO+C2H2 5.000E+13 .000 .00 CH2+O2=>OH+H+CO 5.000E+12 .000 1500.00 CH2+H2<=>H+CH3 5.000E+05 2.000 7230.00 2CH2<=>H2+C2H2 1.600E+15 .000 11944.00 CH2+CH3<=>H+C2H4 4.000E+13 .000 .00 CH2+CH4<=>2CH3 2.460E+06 2.000 8270.00 CH2+CO(+M)<=>CH2CO(+M) 8.100E+11 .500 4510.00 LOW / 2.690E+33 -5.110 7095.00/ TROE/ .5907 275.00 1226.00 5185.00 / H2/2.00/ H2O/6.00/ CH4/2.00/ CO/1.50/ CO2/2.00/ C2H6/3.00/ AR/ .70/ C2H4/3.0/ pC3H4/4.0/ C3H6/4.0/ C3H8/4.0/ CH2+HCCO<=>C2H3+CO 3.000E+13 .000 .00 CH2*+N2<=>CH2+N2 1.500E+13 .000 600.00 CH2*+AR<=>CH2+AR 9.000E+12 .000 600.00 CH2*+O2<=>H+OH+CO 2.800E+13 .000 .00 CH2*+O2<=>CO+H2O 1.200E+13 .000 .00 CH2*+H2<=>CH3+H 7.000E+13 .000 .00 CH2*+H2O(+M)<=>CH3OH(+M) 4.820E+17 -1.160 1145.00 LOW / 1.880E+38 -6.360 5040.00/ TROE/ .6027 208.00 3922.00 10180.0 / H2/2.00/ H2O/6.00/ CH4/2.00/ CO/1.50/ CO2/2.00/ C2H6/3.00/ C2H4/3.0/ pC3H4/4.0/ C3H6/4.0/ C3H8/4.0/ CH2*+H2O<=>CH2+H2O 3.000E+13 .000 .00 CH2*+CH3<=>H+C2H4 1.200E+13 .000 -570.00 CH2*+CH4<=>2CH3 1.600E+13 .000 -570.00 CH2*+CO<=>CH2+CO 9.000E+12 .000 .00 CH2*+CO2<=>CH2+CO2 7.000E+12 .000 .00 CH2*+CO2<=>CO+CH2O 1.400E+13 .000 .00 CH2*+C2H6<=>CH3+C2H5 4.000E+13 .000 -550.00 CH3+O2<=>O+CH3O 3.560E+13 .000 30480.00 CH3+O2<=>OH+CH2O 2.310E+12 .000 20315.00 CH3+H2O2<=>HO2+CH4 2.450E+04 2.470 5180.00 2CH3(+M)<=>C2H6(+M) 6.770E+16 -1.180 654.00 LOW / 3.400E+41 -7.030 2762.00/ TROE/ .6190 73.20 1180.00 9999.00 / H2/2.00/ H2O/6.00/ CH4/2.00/ CO/1.50/ CO2/2.00/ C2H6/3.00/ AR/ .70/ C2H4/3.0/ pC3H4/4.0/ C3H6/4.0/ C3H8/4.0/ 2CH3<=>H+C2H5 6.840E+12 .100 10600.00 CH3+HCO<=>CH4+CO 2.648E+13 .000 .00 CH3+CH2O<=>HCO+CH4 3.320E+03 2.810 5860.00 CH3+CH3OH<=>CH2OH+CH4 3.000E+07 1.500 9940.00 CH3+CH3OH<=>CH3O+CH4 1.000E+07 1.500 9940.00 CH3+C2H4<=>C2H3+CH4 2.270E+05 2.000 9200.00 CH3+C2H6<=>C2H5+CH4 6.140E+06 1.740 10450.00 HCO+H2O<=>H+CO+H2O 1.500E+18 -1.000 17000.00 HCO+M<=>H+CO+M 1.870E+17 -1.000 17000.00 H2/2.00/ H2O/ .00/ CH4/2.00/ CO/1.50/ CO2/2.00/ C2H6/3.00/ HCO+O2<=>HO2+CO 13.45E+12 .000 400.00 CH2OH+O2<=>HO2+CH2O 1.800E+13 .000 900.00 CH3O+O2<=>HO2+CH2O 4.280E-13 7.600 -3530.00 C2H+O2<=>HCO+CO 1.000E+13 .000 -755.00 C2H+H2<=>H+C2H2 5.680E+10 0.900 1993.00 C2H3+O2<=>HCO+CH2O 4.580E+16 -1.390 1015.00 C2H4(+M)<=>H2+C2H2(+M) 8.000E+12 .440 86770.00 LOW / 1.580E+51 -9.300 97800.00/ TROE/ .7345 180.00 1035.00 5417.00 / H2/2.00/ H2O/6.00/ CH4/2.00/ CO/1.50/ CO2/2.00/ C2H6/3.00/ AR/ .70/ C2H4/3.0/ pC3H4/4.0/ C3H6/4.0/ C3H8/4.0/ C2H5+O2<=>HO2+C2H4 8.400E+11 .000 3875.00 HCCO+O2<=>OH+2CO 3.200E+12 .000 854.00 2HCCO<=>2CO+C2H2 1.000E+13 .000 .00 O+CH3=>H+H2+CO 3.370E+13 .000 .00 O+C2H4<=>H+CH2CHO 3.350E+06 1.830 220.00 ! k_opt=0.5*ko O+C2H5<=>H+CH3CHO 1.096E+14 .000 .00 OH+HO2<=>O2+H2O 0.500E+16 .000 17330.00 DUPLICATE OH+CH3=>H2+CH2O 8.000E+09 .500 -1755.00 CH+H2(+M)<=>CH3(+M) 1.970E+12 .430 -370.00 LOW/ 4.820E+25 -2.80 590.0 / TROE/ .578 122.0 2535.0 9365.0 / H2/2.00/ H2O/6.00/ CH4/2.00/ CO/1.50/ CO2/2.00/ C2H6/3.00/ AR/ .70/ C2H4/3.0/ pC3H4/4.0/ C3H6/4.0/ C3H8/4.0/ CH2+O2=>2H+CO2 5.800E+12 .000 1500.00 CH2+O2<=>O+CH2O 2.400E+12 .000 1500.00 CH2+CH2=>2H+C2H2 2.000E+14 .000 10989.00 CH2*+H2O=>H2+CH2O 6.820E+10 .250 -935.00 C2H3+O2<=>O+CH2CHO 1.212E+11 .290 11.00 ! k_opt=0.4*ko C2H3+O2<=>HO2+C2H2 1.337E+06 1.610 -384.00 O+CH3CHO<=>OH+CH2CHO 2.920E+12 .000 1808.00 O+CH3CHO=>OH+CH3+CO 2.920E+12 .000 1808.00 O2+CH3CHO=>HO2+CH3+CO 3.010E+13 .000 39150.00 H+CH3CHO<=>CH2CHO+H2 2.050E+09 1.160 2405.00 H+CH3CHO=>CH3+H2+CO 2.050E+09 1.160 2405.00 OH+CH3CHO=>CH3+H2O+CO 2.343E+10 0.730 -1113.00 HO2+CH3CHO=>CH3+H2O2+CO 3.010E+12 .000 11923.00 CH3+CH3CHO=>CH3+CH4+CO 2.720E+06 1.770 5920.00 H+CH2CO(+M)<=>CH2CHO(+M) 4.865E+11 0.422 -1755.00 LOW/ 1.012E+42 -7.63 3854.0/ TROE/ 0.465 201.0 1773.0 5333.0 / H2/2.00/ H2O/6.00/ CH4/2.00/ CO/1.50/ CO2/2.00/ C2H6/3.00/ AR/ .70/ C2H4/3.0/ pC3H4/4.0/ C3H6/4.0/ C3H8/4.0/ O+CH2CHO=>H+CH2+CO2 1.500E+14 .000 .00 O2+CH2CHO=>OH+CO+CH2O 1.810E+10 .000 .00 O2+CH2CHO=>OH+2HCO 2.350E+10 .000 .00 H+CH2CHO<=>CH3+HCO 2.200E+13 .000 .00 H+CH2CHO<=>CH2CO+H2 1.100E+13 .000 .00 OH+CH2CHO<=>H2O+CH2CO 1.200E+13 .000 .00 OH+CH2CHO<=>HCO+CH2OH 3.010E+13 .000 .00 ! File 2a: A set of Qin (commented) & Scott's C3 (C=3) reactions. ! !=====================! ! ! ! C3 chemistry ! ! ! !=====================! ! ! ***** C2H3O chemistry and additional reactions for C<3 removed. ****** ! CH3 + C2H <=> C3H3 + H 2.41E+13 0.0 0.0 ! Tsang-Hampson ! C2H2 + CH <=> C3H2 + H 3.00E+13 0.0 0.0 ! Warnatz 83 C2H2 + CH2 <=> C3H3 + H 1.20E+13 0.0 6620.0 ! Bohland 86 C2H2 + CH2* <=> C3H3 + H 2.00E+13 0.0 0.0 ! Estimated C2H2 + HCCO <=> C3H3 + CO 1.00E+11 0.0 3000.0 ! Miller-Bowman ! ! ***** Four C1 and C2 reactions removed. ***** ! ! ! Reactions of C3Hx species ! C3H2 + O <=> C2H2 + CO 6.80E+13 0.0 0.0 ! Warnatz 82 !C3H2 + OH <=> H + CO + C2H2 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+13 0.0 0.0 ! Miller-Melius C3H2 + O2 <=> HCCO + H + CO 2.00E+12 0.0 1000.0 ! Miller C3H2 + H <=> C3H3 1.00E+13 0.0 0.0 ! Estimated ! ! Propargyl Reactions ! C3H3 + H <=> pC3H4 0.855E+13 0.0 0.0 ! Est. ! k_opt=0.57*ko ! pC3H4+AR<=>C3H3+H+AR 4.7e+18 0.00 80000. ! Qin_hidaka89 C3H3 + H <=> aC3H4 0.825E+12 0.0 0.0 ! Est. ! k_opt=0.33*ko ! aC3H4+AR<=>C3H3+H+AR 2.00e+18 0.00 80000. ! Qin_hidaka89 ! ! Products reassigned to avoid C3H3 and C3H2 build-up ! 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 1.42E+13 0.0 0.0 ! Miller-Bowman ! k_opt=0.71*ko C3H3 + O2 <=> CH2CO + HCO 4.17E+10 0.0 2868.0 ! Gutman ! k_opt=1.39*ko ! C3H3+O2<=>CH2CO+HCO 1.1e+12 0.00 9219. ! Qin_est C3H3 + HO2 <=> OH + CO + C2H3 8.00E+11 0.0 0.0 ! Estimated C3H3 + HO2 <=> aC3H4 + O2 9.00E+11 0.0 0.0 ! EST-NEW ! k_opt=3*ko C3H3 + HO2 <=> pC3H4 + O2 1.10E+12 0.0 0.0 ! EST-NEw ! k_opt=0.44*ko C3H3 + HCO <=> aC3H4 + CO 2.50E+13 0.0 0.0 ! Estimated C3H3 + HCO <=> pC3H4 + CO 2.50E+13 0.0 0.0 ! Estimated ! aC3H4 + H <=> C3H3 + H2 1.30E+06 2.0 5500.0 ! <=> pC3H4 + H ! aC3H4+H<=>C3H3+H2 1.00e+12 0.00 1500. ! Qin_hidaka89 aC3H4 + H <=> CH3CCH2 9.46E+42 -9.43 11190.0 ! WD 1 atm !aC3H4 + H <=> CH3CCH2 8.47E+43 -9.59 12462.0 ! WD 2 atm !aC3H4 + H <=> CH3CCH2 6.98E+44 -9.70 14032.0 ! WD 5 atm aC3H4 + H <=> aC3H5 1.52E+59 -13.54 26949.0 ! WD 1 atm !aC3H4 + H <=> aC3H5 3.78E+57 -12.98 26785.0 ! WD 2 atm !aC3H4 + H <=> aC3H5 7.34E+54 -12.09 26187.0 ! WD 5 atm ! aC3H5<=>aC3H4+H 1.40e+13 0.00 59992. ! Qin_tsang91 aC3H4 + O <=> C2H4 + CO 2.00E+07 1.8 1000.0 ! Est. See notes ! aC3H4+O<=>CO+C2H4 7.8e+12 0.00 1600. ! Qin_Westbrook84 ! aC3H4+O<=>HCO+C2H3 1.10e-02 4.613 -4243. ! Qin_dagaut92 ! aC3H4+O2<=>C3H3+HO2 4.00e+13 0.00 61500. ! Qin_dagaut92 aC3H4 + OH <=> C3H3 + H2O 5.30E+06 2.0 2000.0 ! Refit to Liu(note ! aC3H4+OH<=>CH2CO+CH3 3.12e+12 0.00 -397. ! Qin_dagaut94 ! aC3H4+OH<=>C3H3+H2O 2.00e+07 2.00 1000. ! Qin_dagaut94 aC3H4 + CH3 <=> C3H3 + CH4 1.30E+12 0.00 7700.0 ! Wu & Kern ! aC3H4+CH3<=>C3H3+CH4 2.00e+12 0.00 7700. ! Qin_hidaka89 aC3H4 + C2H <=> C2H2 + C3H3 1.00E+13 0.0 0.0 ! Estimated/ ! !pC3H4 <=> cC3H4 1.73E+12 0.31 60015.0 ! WD kinf !pC3H4 <=> cC3H4 2.84E+45 -10.45 69284.0 ! WD 0.4 atm pC3H4 <=> cC3H4 1.20E+44 -9.92 69250.0 ! WD 1 atm !pC3H4 <=> cC3H4 5.47E+42 -9.43 69089.0 ! WD 2 atm !pC3H4 <=> cC3H4 3.92E+40 -8.69 68706.0 ! WD 5 atm ! !pC3H4 <=> aC3H4 5.81E+62 -14.63 91211.0 ! WD 0.4 atm pC3H4 <=> aC3H4 10.3E+60 -13.93 91117.0 ! WD 1 atm ! k_opt=2*ko !pC3H4 <=> aC3H4 7.64E+59 -13.59 91817.0 ! WD 2 atm !pC3H4 <=> aC3H4 3.12E+58 -13.07 92680.0 ! WD 5 atm ! pC3H4<=>aC3H4 2.10e+12 0.00 60000. ! Qin_hidaka89 ! !cC3H4 <=> aC3H4 1.98E+12 0.56 42240.0 ! WD kinf !cC3H4 <=> aC3H4 7.59E+40 -9.07 48831.0 ! WD 0.4 atm cC3H4 <=> aC3H4 4.89E+41 -9.17 49594.0 ! WD 1 atm !cC3H4 <=> aC3H4 8.81E+41 -9.15 50073.0 ! WD 2 atm !cC3H4 <=> aC3H4 4.33E+41 -8.93 50475.0 ! WD 5 atm ! pC3H4 + H <=> aC3H4 + H 6.27E+17 -0.91 10079.0 ! WD 1 atm !pC3H4 + H <=> aC3H4 + H 1.50E+18 -1.00 10756.0 ! WD 2 atm !pC3H4 + H <=> aC3H4 + H 1.93E+18 -1.01 11523.0 ! WD 5 atm pC3H4 + H <=> CH3CCH2 1.66E+47 -10.58 13690.0 ! WD 1 atm !pC3H4 + H <=> CH3CCH2 5.04E+47 -10.61 14707.0 ! WD 2 atm !pC3H4 + H <=> CH3CCH2 9.62E+47 -10.55 15910.0 ! WD 5 atm pC3H4 + H <=> aC3H5 4.91E+60 -14.37 31644.0 ! WD 1 atm !pC3H4 + H <=> aC3H5 3.04E+60 -14.19 32642.0 ! WD 2 atm !pC3H4 + H <=> aC3H5 9.02E+59 -13.89 33953.0 ! WD 5 atm !pC3H4 + H <=> C3H3 + H2 1.15E+08 1.9 7530.0 ! <=> C2H6 + H pC3H4 + H <=> C3H3 + H2 1.30E+06 2.0 5500.0 ! Estimated (from Wu and Kern) ! pC3H4+H<=>C3H3+H2 1.0e+12 0.00 1500. ! Qin_hidaka89 ! pC3H4+H<=>C2H2+CH3 1.30e+05 2.5 1000. ! Qin_hidaka89 ! !pC3H4 + C3H3 <=> aC3H4 + C3H3 6.140E+06 1.740 10450. ! Estimate(CH3+C2H6) !pC3H4 + H <=> CH3 + C2H2 1.30E+05 2.5 1000.0 ! Hidaka pC3H4 + O <=> HCCO + CH3 2.04E+13 0.0 2250.0 ! Fontijn/split ! k_opt=2.79*ko ! pC3H4+O<=>HCCO+CH3 6.30e+12 0.00 2010. ! Qin_dagaut94 pC3H4 + O <=> C2H4 + CO 0.58E+13 0.0 2250.0 ! Fontijn/split ! k_opt=0.58*ko !pC3H4 + O <=> C2H3 + HCO 0.73E+13 0.0 2250.0 ! Fontijn/split ! pC3H4+O<=>C2H3+HCO 3.20e+12 0.00 2010. ! Qin_dagaut94 !pC3H4 + O <=> C3H3 + OH 3.45e+04 2.16 4830.0 ! Fontijn ! pC3H4+O<=>CH2CO+CH2 6.40e+12 0.00 2010. ! Qin_dagaut94 ! pC3H4+O2<=>C3H3+HO2 5.00e+12 0.00 51000. ! Qin_dagaut94 !pC3H4 + OH <=> C3H3 + H2O 3.54E+06 2.12 870.0 ! <=> C2H6 + OH (too high) pC3H4 + OH <=> C3H3 + H2O 1.00E+06 2.0 100.0 ! This work ! pC3H4+OH<=>C3H3+H2O 2.00e+07 2.00 1000. ! Qin_dagaut94 ! pC3H4+OH<=>CH2CO+CH3 5.00e-04 4.50 -1000. ! Qin_dagaut94 pC3H4 + C2H <=> C2H2 + C3H3 1.00E+13 0.0 0.0 ! Estimated pC3H4 + CH3 <=> C3H3 + CH4 1.80E+12 0.0 7700.0 ! Wu & Kern ! pC3H4+CH3<=>C3H3+CH4 2.00e+12 0.00 7700. ! Qin_hidaka89 ! ! ! Reactions of propane ! C3H8+H <=> H2+nC3H7 1.30E+06 2.54 6756.0 ! TS3 C3H8+H <=> H2+iC3H7 2.60E+06 2.40 4471.0 ! TS3 ! k_opt=2*ko ! C3H8+H<=>iC3H7+H2 1.26e+08 1.735 4864. ! Qin_yang98 ! C3H8+H<=>nC3H7+H2 1.95e+08 1.827 7463. ! Qin_yang98 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+O<=>iC3H7+OH 4.77e+04 2.71 2106. ! Qin_tsang88 ! C3H8+O<=>nC3H7+OH 1.93e+05 2.68 3716. ! Qin_tsang88 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+OH<=>iC3H7+H2O 1.84e+05 2.38 -573. ! Qin_dagaut92 ! C3H8+OH<=>nC3H7+H2O 4.16e+07 1.74 540. ! Qin_dagaut92 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+O2<=>iC3H7+HO2 3.97e+13 0.00 47688. ! Qin_tsang88 ! C3H8+O2<=>nC3H7+HO2 3.97e+13 0.00 50867. ! Qin_tsang88 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+HO2<=>iC3H7+H2O2 9.63e+03 2.60 13909. ! Qin_tsang88 ! C3H8+HO2<=>nC3H7+H2O2 4.76e+04 2.55 16492. ! Qin_tsang88 C3H8+CH3 <=> CH4+nC3H7 9.03E-01 3.65 7153.0 ! TS3 C3H8+CH3 <=> CH4+iC3H7 1.51E+00 3.46 5480.0 ! TS3 ! CH3+C3H8<=>iC3H7+CH4 1.51e+00 3.46 5480. ! Qin_tsang88 ! CH3+C3H8<=>nC3H7+CH4 9.03e-01 3.65 7153. ! Qin_tsang88 ! C2H3+C3H8<=>C2H4+iC3H7 1.02e+03 3.10 8828. ! Qin_tsang88 ! C2H3+C3H8<=>C2H4+nC3H7 6.03e+02 3.30 10501. ! Qin_tsang88 ! C2H5+C3H8<=>C2H6+iC3H7 1.20e+00 3.46 7467. ! Qin_tsang88 ! C2H5+C3H8<=>C2H6+nC3H7 9.04e-01 3.65 9140. ! Qin_tsang88 ! C3H8+aC3H5<=>iC3H7+C3H6 7.87e+01 3.30 18169. ! Qin_tsang91 ! C3H8+aC3H5<=>nC3H7+C3H6 2.35e+02 3.30 19842. ! Qin_tsang91 ! iC3H7+C3H8<=>nC3H7+C3H8 8.44e-03 4.20 8684. ! Qin_tsang88 ! CH3O+C3H8<=>CH3OH+iC3H7 1.45e+11 0.00 4570. ! Qin_tsang88 ! CH3O+C3H8<=>CH3OH+nC3H7 4.34e+11 0.00 6458. ! Qin_tsang88 ! ! Reactions of n-propyl ! 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/ C2H4/3.0/ pC3H4/4.0/ C3H6/4.0/ C3H8/4.0/ !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+O2<=>C3H6+HO2 1.00e+12 0.00 5019. ! Qin_tsang88 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 ! ! kinf : TS3 recommendation ! ko: scaled such that Pr(nC3H7+CH3) <=> Pr(C2H5+CH3) 500cm-1 ! Fc: assumed equal to Fc(C2H5+CH3) ! ! 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/ C2H4/3.0/ pC3H4/4.0/ C3H6/4.0/ C3H8/4.0/ !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+O2<=>C3H6+HO2 1.26e+11 0.00 0. ! Qin_tsang88 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 propene ! 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/ C2H4/3.0/ pC3H4/4.0/ C3H6/4.0/ C3H8/4.0/ ! nC3H7<=>H+C3H6 1.26e+14 0.00 37000. ! Qin_westbrook84 ! nC3H7<=>CH3+C2H4 1.20e+13 0.00 30300. ! Qin_tsang88 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/ C2H4/3.0/ pC3H4/4.0/ C3H6/4.0/ C3H8/4.0/ ! iC3H7<=>H+C3H6 1.60e+13 0.00 35766. ! Qin_tsang88 ! iC3H7<=>CH3+C2H4 2.00e+10 0.00 29500. ! Qin_westbrook84 ! !C3H6+H <=> C2H4+CH3 17.6E+16 -1.05 6461.0 ! TS5 0.1 atm*2 C3H6+H <=> C2H4+CH3 25.76E+21 -2.39 11180.0 ! TS5 1 atm*2 ! k_opt=1.61*ko !C3H6+H <=> C2H4+CH3 6.60E+24 -3.04 15610.0 ! TS5 10 atm*2 ! C3H6+H<=>CH3+C2H4 7.23e+12 0.00 1301. ! Qin_tsang91 ! C3H6+H <=> aC3H5+H2 0.85E+05 2.50 2490.0 ! TS5 k(a) ! k_opt=0.5*ko ! C3H6+H<=>aC3H5+H2 1.70e+05 2.50 2492. ! Qin_tsang92 C3H6+H <=> CH3CCH2+H2 4.00E+05 2.50 9790.0 ! TS5 k(b) C3H6+O <=> CH2CO+CH3+H 1.20E+08 1.65 327.0 ! TS5 k(a+b) tot C3H6+O <=> C2H5+HCO 3.50E+07 1.65 -972.0 ! TS5 k(c) ! C3H6+O<=>C2H5+HCO 1.20e+11 0.70 8959. ! Qin_tsang91 C3H6+O <=> aC3H5+OH 1.80E+11 0.70 5880.0 ! TS5 k(d) C3H6+O <=> CH3CCH2+OH 6.00E+10 0.70 7630.0 ! TS5 K(f) ! C3H6+O<=>C2H4+CH2O 5.89e+13 0.00 5000. ! Qin_westbrook84 ! C3H6+O<=>CH3+CH3+CO 1.17e+13 0.00 600. ! Qin_westbrook84 C3H6+OH <=> aC3H5+H2O 3.97E+06 2.00 -298.0 ! TS5 ! k_opt=1.28*ko C3H6+OH <=> CH3CCH2+H2O 1.10E+06 2.00 1450.0 ! TS5 ! C3H6+OH<=>C2H5+CH2O 7.90e+12 0.00 0. ! Qin_cathonnet81 ! C3H6+OH<=>CH3+CH3CHO 3.47e+11 0.00 0. ! Qin_westbrook84 ! C3H6+OH<=>aC3H5+H2O 3.12e+06 2.00 -298. ! Qin_tsang91 ! C3H6+OH<=>CH3CHCH+H2O 2.14e+06 2.00 2778. ! Qin_tsang91 ! C3H6+OH<=>CH3CCH2+H2O 1.11e+06 2.00 1451. ! Qin_tsang91 ! CH3CHCH+H<=>aC3H4+H2 3.33e+12 0.00 0. ! Qin_dagaut88 ! CH3CHCH+O<=>CH2CO+CH3 1.807e+14 0.00 0. ! Qin_dagaut88 ! CH3CHCH+CH3<=>aC3H4+CH4 1.000e+11 0.00 0. ! Qin_dagaut88 ! CH3CHCH+C2H3<=>aC3H4+C2H4 1.000e+11 0.00 0. ! Qin_dagaut88 ! CH3CHCH+C2H5<=>aC3H4+C2H6 1.000e+11 0.00 0. ! Qin_dagaut88 ! CH3CCH2+H<=>aC3H4+H2 3.33e+12 0.00 0. ! Qin_dagaut88 C3H6+HO2 <=> aC3H5+H2O2 9.60E+03 2.60 13910.0 ! TS5 C3H6+CH3 <=> aC3H5+CH4 2.20E+00 3.50 5675.0 ! TS5 k(c) ! C3H6+CH3<=>aC3H5+CH4 2.21e+00 3.50 5675. ! Qin_tsang91 C3H6+CH3 <=> CH3CCH2+CH4 8.40E-01 3.50 11660.0 ! TS5 k(e) ! C3H6+C2H5<=>aC3H5+C2H6 2.23e+00 3.50 6637. ! Qin_tsang91 ! ! Reactions of allyl ! aC3H5+H(+M) <=> C3H6(+M) 3.70E+14 0.00 0.0 ! TS5 600cm-1 ! k_opt=1.85*ko LOW / 1.33E+60 -12.00 5967.8 / 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/ C2H4/3.0/ pC3H4/4.0/ C3H6/4.0/ C3H8/4.0/ ! C3H6<=>aC3H5+H 2.50e+15 0.00 86679. ! Qin_tsang91 ! aC3H5+H <=> aC3H4+H2 1.80E+13 0.00 0.0 ! TS5 k(c) ! aC3H5+H<=>aC3H4+H2 1.81e+13 0.00 0. ! Qin_tsang91 aC3H5+O <=> C2H3CHO+H 6.00E+13 0.00 0.0 ! TS5 !aC3H5+OH <=> C2H3CHO+H+H 5.30E+37 -6.71 29306.0 ! TS5, 0.1 atm aC3H5+OH <=> C2H3CHO+H+H 4.20E+32 -5.16 30126.0 ! TS5, 1 atm !aC3H5+OH <=> C2H3CHO+H+H 1.60E+20 -1.56 26330.0 ! TS5, 10 atm ! C2H3+HCO <=> C2H3CHO 1.80E+13 0.00 0.0 ! TS5 C2H3CHO+H <=> C2H4+HCO 1.08E+12 0.454 1820.00 ! <=>C2H4+H (kinf) C2H3CHO+O <=> C2H3+OH+CO 3.00E+13 0.00 3540.00 ! <=>CH2O+O C2H3CHO+O <=> CH2O+CH2CO 1.90E+07 1.80 220.00 ! <=>C2H4+O C2H3CHO+OH <=> C2H3+H2O+CO 3.43E+09 1.18 -447.00 ! <=>CH2O+OH ! aC3H5+OH <=> aC3H4+H2O 6.00E+12 0.00 0.0 ! TS5 k(a) aC3H5+O2 <=> aC3H4+HO2 4.99E+15 -1.40 22428.0 ! Bozzelli, 1 atm !aC3H5+O2 <=> aC3H4+HO2 2.18E+21 -2.85 30755.0 ! Bozzelli, 10 atm ! aC3H5+O2<=>aC3H4+HO2 1.21e+12 0.00 13551. ! Qin_tsang91 aC3H5+O2 <=> CH3+CO+CH2O 1.19E+15 -1.01 20128.0 ! Bozzelli, 1 atm !aC3H5+O2 <=> CH3+CO+CH2O 7.14E+15 -1.21 21046.0 ! Bozzelli, 10 atm aC3H5+O2 <=> C2H3CHO+OH 1.82E+13 -0.41 22859.0 ! Bozzelli, 1 atm !aC3H5+O2 <=> C2H3CHO+OH 2.47E+13 -0.45 23017.0 ! Bozzelli, 10 atm ! aC3H5+HO2 <=> C3H6+O2 2.66E+12 0.00 0.0 ! CEC aC3H5+HO2 <=> OH+C2H3+CH2O 6.60E+12 0.00 0.0 ! CEC !aC3H5+HO2 <=> OH+C2H3+CH2O 3.00E+12 0.00 0.0 ! CEC/2.21 ! aC3H5+HCO <=> C3H6+CO 6.00E+13 0.00 0.0 ! TS5 ! aC3H5+CH3 <=> aC3H4+CH4 3.00E+12 -0.32 -131.0 ! TS5 k(a) ! aC3H5+CH3<=>aC3H4+CH4 3.01e+12 -0.32 -131. ! Qin_tsang91 aC3H5+aC3H5 <=> C3H6 + aC3H4 1.00E+13 0.00 0.0 ! Estimated aC3H5 <=> CH3CCH2 7.06E+56 -14.08 75868.0 ! WD 1 atm !aC3H5 <=> CH3CCH2 4.80E+55 -13.59 75949.0 ! WD 2 atm !aC3H5 <=> CH3CCH2 4.86E+53 -12.81 75883.0 ! WD 5 atm ! aC3H5+C2H3<=>aC3H4+C2H4 2.41+12 0.00 0. ! Qin_tsang91 ! aC3H5+C2H3<=>C3H6+C2H2 4.82+12 0.00 0. ! Qin_tsang91 ! aC3H5+C2H5<=>aC3H4+C2H6 9.64e+11 0.00 -131. ! Qin_tsang91 ! aC3H5+C2H5<=>C3H6+C2H4 2.59e+12 0.00 -131. ! Qin_tsang91 ! ! Reactions of propen-2-yl ! CH3CCH2+H <=> pC3H4+H2 3.34E+12 0.00 0.0 ! PW CH3CCH2+O <=> CH3+CH2CO 6.00E+13 0.00 0.0 ! Estimated CH3CCH2+OH <=> CH3+CH2CO+H 5.00E+12 0.00 0.0 ! Estimated !CH3CCH2+O2 <=> CH3CHO+HCO 1.00E+11 0.00 0.0 ! PW/changed CH3CCH2+O2 <=> CH3+CO+CH2O 1.00E+11 0.00 0.0 ! PW/changed CH3CCH2+HO2 <=> CH3+CH2CO+OH 2.00E+13 0.00 0.0 ! Estimated CH3CCH2+HCO <=> C3H6+CO 9.00E+13 0.00 0.0 ! Estimated CH3CCH2+CH3 <=> pC3H4+CH4 1.00E+11 0.00 0.0 ! PW ! ! ***** Five reactions of CH3CHO removed. ***** ! ! ! ***** Eight reactions of CH3CO removed. ***** ! ! ! Recombination reactions of C1 and C2 species ! ! ***** Reaction CH3+HCO <=> CH3CHO removed. ***** ! CH3+C2H2 <=> pC3H4+H 1.28E+09 1.10 13644.0 ! WD 1 atm ! k_opt=0.5*ko !CH3+C2H2 <=> pC3H4+H 2.07E+10 0.85 14415.0 ! WD 2 atm !CH3+C2H2 <=> pC3H4+H 2.51E+11 0.56 15453.0 ! WD 5 atm CH3+C2H2 <=> aC3H4+H 5.14E+09 0.86 22153.0 ! WD 1 atm !CH3+C2H2 <=> aC3H4+H 1.33E+10 0.75 22811.0 ! WD 2 atm !CH3+C2H2 <=> aC3H4+H 9.20E+10 0.54 23950.0 ! WD 5 atm CH3+C2H2 <=> CH3CCH2 4.99E+22 -4.39 18850.0 ! WD 1 atm !CH3+C2H2 <=> CH3CCH2 6.00E+23 -4.60 19571.0 ! WD 2 atm !CH3+C2H2 <=> CH3CCH2 7.31E+25 -5.06 21150.0 ! WD 5 atm CH3+C2H2 <=> aC3H5 2.68E+53 -12.82 35730.0 ! WD 1 atm !CH3+C2H2 <=> aC3H5 3.64E+52 -12.46 36127.0 ! WD 2 atm !CH3+C2H2 <=> aC3H5 1.04E+51 -11.89 36476.0 ! WD 5 atm ! CH3+C2H3(+M) <=> C3H6(+M) 2.50E+13 0.00 0.0 ! TS1 600cm-1 LOW / 4.27E+58 -11.94 9769.8 / 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/ C2H4/3.0/ pC3H4/4.0/ C3H6/4.0/ C3H8/4.0/ ! C3H6<=>C2H3+CH3 8.39e+14 0.00 87990. ! Qin_hidaka92 ! !CH3+C2H3 <=> aC3H5+H 1.00E+36 -6.28 22442.0 ! TS1 0.1 atm CH3+C2H3 <=> aC3H5+H 1.50E+24 -2.83 18618.0 ! TS1 1 atm !CH3+C2H3 <=> aC3H5+H 3.00E+08 1.65 12027.0 ! TS1 10 atm ! CH3+C2H4 <=> nC3H7 3.30E+11 0.00 7700.0 ! KP CH3+C2H5(+M) <=> C3H8(+M) 9.60E+14 -0.50 0.0 ! TS3 TS1 500cm-1 ! k_opt=1.96*ko 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/ C2H4/3.0/ pC3H4/4.0/ C3H6/4.0/ C3H8/4.0/ ! C3H8<=>CH3+C2H5 2.58d+232 -60.2 254600. ! Qin_2.6_to_4.2_atm !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 ! ! File 3a: A set of Scott's C>3 (C <=> 4, 5, 6) reactions. ! !<=><=><=><=><=><=><=><=><=><=><=><=><=><=><=><=><=><=><=><=>! ! ! ! C4-up chemistry ! ! ! !<=><=><=><=><=><=><=><=><=><=><=><=><=><=><=><=><=><=><=><=>! ! C2H2 + C2H <=> C4H2 + H 9.60E+13 0.0 0.0 ! See notes C2H2 + C2H <=> n-C4H3 4.50E+37 -7.68 7100.0 ! RRKM, 760 t C2H2 + C2H <=> i-C4H3 2.60E+44 -9.47 14650.0 ! RRKM, 760 t C2H2 + C2H3 <=> C4H4 + H 2.00E+18 -1.68 10600. ! 760 t C2H2 + C2H3 <=> n-C4H5 9.3E+38 -8.76 12000. ! 760 t C2H2 + C2H3 <=> i-C4H5 1.6E+46 -10.98 18600. ! 760 t C2H4 + C2H <=> C4H4 + H 1.20E+13 0.0 0.0 ! Tsang C2H4 + C2H3 <=> C4H6 + H 2.8E+21 -2.44 14720.0 ! 760 t C2H3 + C2H3 <=> C4H6 1.5E+42 -8.84 12483. ! RRKM 760 t C2H3 + C2H3 <=> i-C4H5 + H 1.2E+22 -2.44 13654. ! RRKM 760 t C2H3 + C2H3 <=> n-C4H5 + H 2.4E+20 -2.04 15361. ! RRKM 760 t ! ! Reactions of C3Hx species ! 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 ! ! Products reassigned to avoid C3H3 and C3H2 build-up ! 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/ C2H4/3.0/ pC3H4/4.0/ C3H6/4.0/ C3H8/4.0/ ! A1- + pC3H4 <=> A1 + C3H3 2.000E+12 0.0 15000.0 A1- + aC3H4 <=> A1 + C3H3 2.000E+12 0.0 15000.0 ! ! Reactions of C4H2 ! C4H2 + H <=> n-C4H3 1.10E+42 -8.72 15300.0 ! RRKM, 760 t C4H2 + H <=> i-C4H3 1.10E+30 -4.92 10800.0 ! RRKM, 760 t C4H2 + O <=> C3H2 + CO 2.70E+13 0.0 1720.0 ! Wellman C4H2 + OH <=> H2C4O + H 6.60E+12 0.0 -410.0 ! Perry? H2C4O + H <=> C2H2 + HCCO 5.00E+13 0.0 3000.0 ! Miller-Melius H2C4O + OH <=> CH2CO + HCCO 1.00E+07 2.0 2000.0 ! Miller-Melius ! ! Reactions of C4H3 and C4H4 ! n-C4H3 <=> i-C4H3 4.10E+43 -9.49 53000.0 ! RRKM, 760 t n-C4H3 + H <=> i-C4H3 + H 2.50E+20 -1.67 10800.0 ! RRKM, 760 t n-C4H3 + H <=> C2H2 + C2H2 6.30E+25 -3.34 10014.0 ! RRKM, 760 t i-C4H3 + H <=> C2H2 + C2H2 2.80E+23 -2.55 10780.0 ! RRKM, 760 t n-C4H3 + H <=> C4H4 2.00E+47 -10.26 13070.0 ! RRKM, 760 t i-C4H3 + H <=> C4H4 3.40E+43 -9.01 12120.0 ! RRKM, 760 t n-C4H3 + H <=> C4H2 + H2 3.00E+13 0.00 0.0 ! 0.5*C2H3+H i-C4H3 + H <=> C4H2 + H2 6.00E+13 0.00 0.0 ! C2H3+H n-C4H3 + OH <=> C4H2 + H2O 2.00E+12 0.00 0.0 i-C4H3 + OH <=> C4H2 + H2O 4.00E+12 0.00 0.0 i-C4H3 + O2 <=> HCCO + CH2CO 7.86E+16 -1.80 0.0 ! Gutman ! C4H4 + H <=> n-C4H5 1.3E+51 -11.92 16500. ! 760 t C4H4 + H <=> i-C4H5 4.9E+51 -11.92 17700. ! 760 t C4H4 + H <=> n-C4H3 + H2 6.65E+05 2.53 12240.0 ! <=>(C2H4+H)/2 C4H4 + H <=> i-C4H3 + H2 3.33E+05 2.53 9240.0 ! -3kcal/mol, /4 C4H4 + OH <=> n-C4H3 + H2O 3.10E+07 2.0 3430.0 ! <=> C4H6 + OH C4H4 + OH <=> i-C4H3 + H2O 1.55E+07 2.0 430.0 ! -3kcal/mol, /2 ! ! 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 + O2 <=> C2H4 + CO + HCO 4.16E+10 0.00 2500. ! Gutman i-C4H5 + O2 <=> CH2CO + CH2CHO 7.86E+16 -1.80 0.0 ! <=>i-C4H3+O2 n-C4H5 + HCO <=> C4H6 + CO 9.00E+13 0.0 0. ! Estimated i-C4H5 + HCO <=> C4H6 + CO 9.00E+13 0.0 0. ! Estimated ! 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 2000.0 ! Est. C4H6+O <=> HCO+aC3H5 6.00E+08 1.45 -860.0 ! Fontijn 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 ! ! 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 <=> C4H6 1.00E+13 0.0 65000.0 ! Estimated ! ! 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 C3H3 + C3H3 <=> A1- + H 10.20E+12 0.0 0.0 ! k_opt=2.04*ko C3H3 + C3H3 <=> A1 5.780E+12 0.0 0.0 ! k_opt=2.89*ko 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 ! ! 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/ C2H4/3.0/ pC3H4/4.0/ C3H6/4.0/ C3H8/4.0/ ! ! 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 2.10E+12 0.0 7470.0 ! LIN A1- + O2 <=> C6H5O + O 2.60E+13 0.00 6120.0 ! (Frank et al.) ! !C6H5O <=> CO + C5H5 2.51E+11 0.0 43900.0 ! LIN 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/ H2/2.0/ H2O/6.0/ CH4/2.0/ CO/1.5/ CO2/2.0/ C2H6/3.0/ C2H4/3.0/ pC3H4/4.0/ C3H6/4.0/ C3H8/4.0/ ! 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/ H2/2.0/ H2O/6.0/ CH4/2.0/ CO/1.5/ CO2/2.0/ C2H6/3.0/ C2H4/3.0/ pC3H4/4.0/ C3H6/4.0/ C3H8/4.0/ 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 ! 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/ C2H4/3.0/ pC3H4/4.0/ C3H6/4.0/ C3H8/4.0/ ! ! Reactions of 1-butene ! !C4H81+H <=> C2H4+C2H5 17.6E+16 -1.05 6461.0 ! <=>(C3H6+H) TS5 0.1 atm*2 C4H81+H <=> C2H4+C2H5 16.0E+21 -2.39 11180.0 ! <=>(C3H6+H) TS5 1 atm*2 !C4H81+H <=> C2H4+C2H5 6.60E+24 -3.04 15610.0 ! <=>(C3H6+H) TS5 10 atm*2 C4H81+H <=> C3H6+CH3 32.0E+21 -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 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) ! ! Recombination reactions of C1 and C2 species ! !C2H3+C2H4 <=> C4H7 1.21E+05 2.33 3680.0 ! HW inf & !C2H3+C2H4 <=> C4H7 1.23E+35 -7.76 9930.0 ! HW 0.1 atm C2H3+C2H4 <=> C4H7 7.93E+38 -8.47 14220.0 ! HW 1 atm !C2H3+C2H4 <=> C4H7 2.99E+36 -7.40 15480.0 ! HW 10 atm ! 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/ C2H4/3.0/ pC3H4/4.0/ C3H6/4.0/ C3H8/4.0/ ! 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) ! ! 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) ! KP Kerr and Parsonage 1972 review ! Cvetanovic Cvetanovic, R.J. J. Phys. Chem. Ref. Data 16:261, 1987. ! END