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 C2H3 C2H4 C2H5 C2H6 HCCO CH2CO HCCOH ! AR N2 ! C2H3O C2O C3H2 C3H3 pC3H4 aC3H4 C4H C4H2 H2C4O n-C4H3 i-C4H3 C4H4 n-C4H5 i-C4H5 C4H6 C4H612 C5H2 C5H3 C6H C6H2 C6H3 l-C6H4 c-C6H4 n-C6H5 i-C6H5 l-C6H6 n-C6H7 i-C6H7 c-C6H7 C6H8 A1 A1- C6H5O C6H5OH C5H6 C5H5 C5H5O C5H4OH C5H4O ! C4H10 iC4H10 pC4H9 sC4H9 tC4H9 iC4H9 C4H81 C4H82 iC4H8 C4H7 iC4H7 C3H8 nC3H7 iC3H7 C3H6 aC3H5 sC3H5 CH3CHO CH3CO CH3COCH3 C2H3CHO END REACTIONS !=========================================================================! ! ! ! (1) Sun, C. J., Sung, C. J., Wang, H., and Law, C. K. "On the Structure ! ! of Nonsooting Counterflow Ethylene and Acetylene Diffusion Flames." ! ! Combustion and Flame, 107: 321-335 (1996). ! ! ! ! (2) Wang, H., and Frenklach, M. "A Detailed Kinetic Modeling Study of ! ! PAH Formation in Laminar Premixed Acetylene and Ethylene Flames." ! ! Combustion and Flame, 110: 173-221 (1997). ! ! ! ! (3) Wang, H., Hahn, T. O., Sung, C. J., and Law, C. K., "Detailed ! ! Oxidation Kinetics and Flame Inhibition Effects of Chloromethane," ! ! Combustion and Flame, 105: 291-307 (1996). ! ! ! !=========================================================================! ! ! ! Note: The C1 and C2 chemistry is applicable for both subatmospheric ! ! and elevated pressures. ! ! The chemistry for C3 and larger species can be used only at a ! ! pressure of 1 atm. ! ! ! !=========================================================================! ! ! ! C1 and C2 chemistry is taken from GRI-MECH version 1.2 ! ! ! ! Changes: ! ! ! ! (1) C2H + H2 = C2H2 + H ---> k updated based on new measurments ! ! ! ! (2) To lower C2H4 flame speeds, the following reactions from GRI-MECH ! ! are modified ! ! ! ! C2H3 + H = C2H2 + H2 ---> increased to 6.0E+13 ! ! C2H3 + O = CH2CO + H ---> increased to 6.0E+13 ! ! C2H4 + OH = C2H3 + H2O ---> divided by 2 ! HO2 + OH = H2O + O2 ---> multiplied by 1.6 (see also GRIMech 1.2a ! ! ! (3) CH2 + O2 = HCO + OH ---> CH2 + O2 = CO2 + H + H ! with the same rate coefficient to ! *** Unchnaged **** boost up CO2 and H concentrations in ! Su too large (C2H2&C2H4) low-pressure acetylene flames. ! ! ! ! (4) C2H3 + O2 = HCO + CH2O ---> rate coefficients of Bozelli-Dean used. ! ! additional reaction channels for C2H3O added. ! ! reason: to properly account for C2H3 oxidation near main flame zone ! ! ! ! (5) GRI-Mech 1.2a - A quick fix of GRI-Mech 1.2 for the lowered flame ! ! speed data at phi = 0.67. ! ! ! ! (a) k(H+O2+H2O=HO2+H2O) * 1.75 ! ! (b) k(OH+HO2=O2+H2O) * 1.6 ! ! (c) k(HO2+CH3=OH+CH3O) * 0.67 ! ! (d) k(CH3+O2=CH3O+O) * 1.15 ! ! (e) k(HCO+H2O=H+CO+H2O) * 1.5 ! ! ! ! (6) k(H+O2+N2=HO2+N2) changed to Stanford new data ! ! ! ! (7) Additional C2H5 chemistry from Bozzelli and Tsang ! ! ! ! ! ! ! !=========================================================================! ! ! ! Fuel-rich chemistry - aromatics formation and growth ! ! ! ! *** C4 and higher "linear" species: H-abstraction by OH ! ! ! ! A refit to Liu's expression with n=2 (assumed equal to k(C2H4+OH) ! ! gives C4H6 + OH = i-C4H5 + H2O 3.1E+6, 2.0, 430.0 (cal/mol) ! ! Thus, each C-H to produce i-CxHy is 1.55E+06, 2.0, 430 (cal/mol) ! ! each C-H to produce n-CxHy is 1.55E+06, 2.0,3430 (cal/mol) ! ! with + 3cal/mol assumed. ! ! ! ! *** C4 and higher "lineat species: H-abstraction by H ! ! ! ! k = k(C2H4 + H) per H atom for n-CxHy + H2 and ! ! E-3kcal/mol for i-CxHy + H2 products. ! ! ! !=========================================================================! ! ! ! BUTANE, PROPANE MECHANISM ! ! ! ! This mechanism does not include the reaction chemistry ! of R-O-O and R-O species, where R = C3 and C4, thus is expected ! to work only under high-temperature, low and intermediate- ! pressure regions. ! ! The C3 and C4 chemistry is taken mainly from Tsang's compilation. ! !=========================================================================! ! ! C4H10 n-butane CH3CH2CH2CH3 ! iC4H10 i-butane CH(CH3)3 ! pC4H9 1-butyl CH3CH2CH2CH2 ! sC4H9 2-butyl CH3CH2CHCH3 ! tC4H9 t-butyl C(CH3)3 ! iC4H9 i-butyl CH2CH(CH3)2 ! C4H81 1-butene CH3CH2CHCH2 ! C4H82 2-butene CH3CHCHCH3 ! iC4H8 i-butene H2C=C(CH3)2 ! C4H7 1-buten-3-yl CH3CHCHCH2 ! iC4H7 2-methylpropen-3-yl H2C=C(CH3)(CH2) ! C4H6 1,3-butadiene CH2CHCHCH2 ! iC4H5 1,3-butadiene-2-yl CH2CHCCH2 ! C3H8 propane CH3CH2CH3 ! nC3H7 prop-1-yl CH3CH2CH2 ! iC3H7 prop-2-yl CH3CHCH3 ! C3H6 propene CH3CHCH2 ! aC3H5 allyl CH2CHCH2 ! sC3H5 propen-2-yl CH3CCH2 ! !=========================================================================! ! ! Rearanged GRI-12 reaction order ! ! Reactions of H2/O2 ! H+O2 = O+OH 8.300E+13 0.000 14413.00 O+H2 = H+OH 5.000E+04 2.670 6290.00 OH+H2 = H+H2O 2.160E+08 1.510 3430.00 OH+OH = O+H2O 3.570E+04 2.400 -2110.00 H+H+M = H2+M 1.000E+18 -1.000 0.00 H2/0.0/ H2O/0.0/ CH4/2.0/ CO2/0.0/ C2H6/3.00/ AR/0.63/ H+H+H2 = H2+H2 9.000E+16 -0.600 0.00 H+H+H2O = H2+H2O 6.000E+19 -1.250 0.00 H+H+CO2 = H2+CO2 5.500E+20 -2.000 0.00 H+OH+M = H2O+M 2.200E+22 -2.000 0.00 H2/0.73/ H2O/3.65/ CH4/2.0/ C2H6/3.0/ AR/0.38/ O+H+M = OH+M 5.000E+17 -1.000 0.00 H2/2.0/ H2O/6.0/ CH4/2.0/ CO/1.5/ CO2/2.0/ C2H6/3.0/ AR/0.7/ O+O+M = O2+M 1.200E+17 -1.000 0.00 H2/ 2.4/ H2O/15.4/ CH4/ 2.0/ CO/ 1.75/ CO2/ 3.6/ C2H6/ 3.0/ AR/ 0.83/ H+O2+M = HO2+M 2.800E+18 -0.860 0.00 O2/0.0/ H2O/0.0/ CO/0.75/ CO2/1.5/ C2H6/1.5/ N2/0.0/ AR/0.0/ H+O2+O2 = HO2+O2 3.000E+20 -1.720 0.00 ! GRI-Mech 1.2a H+O2+H2O<=>HO2+H2O 1.652E+19 -0.760 0.00 ! New Stanford measurement H+O2+N2 = HO2+N2 2.600E+19 -1.240 0.00 H+O2+AR = HO2+AR 7.000E+17 -0.800 0.00 OH+OH(+M) = H2O2(+M) 7.400E+13 -0.370 0.00 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/ ! ! Reactions of HO2 ! HO2+H = O+H2O 3.970E+12 0.000 671.00 HO2+H = O2+H2 2.800E+13 0.000 1068.00 HO2+H = OH+OH 1.340E+14 0.000 635.00 HO2+O = OH+O2 2.000E+13 0.000 0.00 ! ! Multiplied by 1.5 to lowered C2H4 flame speeds + GRI-Mech 1.2a ! !HO2+OH = O2+H2O 2.900E+13 0.000 -500.00 HO2+OH = O2+H2O 4.640E+13 0.000 -500.00 HO2+HO2 = O2+H2O2 1.300E+11 0.000 -1630.00 DUPLICATE HO2+HO2 = O2+H2O2 4.200E+14 0.000 12000.00 DUPLICATE ! ! Reactions of H2O2 ! H2O2+H = HO2+H2 1.210E+07 2.000 5200.00 H2O2+H = OH+H2O 1.000E+13 0.000 3600.00 H2O2+O = OH+HO2 9.630E+06 2.000 4000.00 H2O2+OH = HO2+H2O 1.750E+12 0.000 320.00 DUPLICATE H2O2+OH = HO2+H2O 5.800E+14 0.000 9560.00 DUPLICATE ! ! Reactions of CO/CO2 ! CO+O+M = CO2+M 6.020E+14 0.000 3000.00 H2/2.0/ O2/6.0/ H2O/6.0/ CH4/2.0/ CO/1.5/ CO2/3.5/ C2H6/3.0/ AR/0.5/ CO+OH = CO2+H 4.760E+07 1.228 70.00 CO+H2(+M) = CH2O(+M) 4.300E+07 1.500 79600.00 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/ CO+O2 = CO2+O 2.500E+12 0.000 47800.00 CO+HO2 = CO2+OH 1.500E+14 0.000 23600.00 ! ! Reactions of C ! C+OH = CO+H 5.000E+13 0.000 0.00 C+O2 = CO+O 5.800E+13 0.000 576.00 ! ! Reactions of CH ! CH+H = C+H2 1.100E+14 0.000 0.00 CH+O = CO+H 5.700E+13 0.000 0.00 CH+OH = HCO+H 3.000E+13 0.000 0.00 CH+H2 = CH2+H 1.107E+08 1.790 1670.00 CH+H2O = CH2O+H 5.710E+12 0.000 -755.00 CH+O2 = HCO+O 3.300E+13 0.000 0.00 CH+CO(+M) = HCCO(+M) 5.000E+13 0.000 0.00 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/ CH+CO2 = HCO+CO 3.400E+12 0.000 690.00 ! ! Reactions of HCO ! HCO+H(+M) = CH2O(+M) 1.090E+12 0.480 -260.00 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/ HCO+H = CO+H2 7.340E+13 0.000 0.00 HCO+O = CO+OH 3.000E+13 0.000 0.00 HCO+O = CO2+H 3.000E+13 0.000 0.00 HCO+OH = CO+H2O 5.000E+13 0.000 0.00 ! beta(H2O) = 18 -- GRI-Mech 1.2a HCO+M = CO+H+M 1.870E+17 -1.000 17000.00 H2/2.0/ H2O/18.0/ CH4/2.0/ CO/1.5/ CO2/2.0/ C2H6/3.0/ HCO+O2 = CO+HO2 7.600E+12 0.000 400.00 ! ! Reactions of CH2(triplet) ! CH2+H(+M) = CH3(+M) 2.500E+16 -0.800 0.00 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/ CH2+O = HCO+H 8.000E+13 0.000 0.00 CH2+OH = CH2O+H 2.000E+13 0.000 0.00 CH2+OH = CH+H2O 1.130E+07 2.000 3000.00 CH2+H2 = H+CH3 5.000E+05 2.000 7230.00 ! ! Products changed, see Wang & Frenklach, C&F, 110: 173-221 (1997). ! ** unchanged ** CH2+O2 = HCO+OH 1.320E+13 0.000 1500.00 CH2+HO2 = CH2O+OH 2.000E+13 0.000 0.00 CH2+C = C2H+H 5.000E+13 0.000 0.00 CH2+CO(+M) = CH2CO(+M) 8.100E+11 0.500 4510.00 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/ CH2+CH = C2H2+H 4.000E+13 0.000 0.00 CH2+CH2 = C2H2+H2 3.200E+13 0.000 0.00 ! ! Reactions of CH2(singlet) ! CH2*+N2 = CH2+N2 1.500E+13 0.000 600.00 CH2*+AR = CH2+AR 9.000E+12 0.000 600.00 CH2*+H = CH+H2 3.000E+13 0.000 0.00 CH2*+O = CO+H2 1.500E+13 0.000 0.00 CH2*+O = HCO+H 1.500E+13 0.000 0.00 CH2*+OH = CH2O+H 3.000E+13 0.000 0.00 CH2*+H2 = CH3+H 7.000E+13 0.000 0.00 CH2*+O2 = H+OH+CO 2.800E+13 0.000 0.00 CH2*+O2 = CO+H2O 1.200E+13 0.000 0.00 CH2*+H2O(+M) = CH3OH(+M) 2.000E+13 0.000 0.00 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/ CH2*+H2O = CH2+H2O 3.000E+13 0.000 0.00 CH2*+CO = CH2+CO 9.000E+12 0.000 0.00 CH2*+CO2 = CH2+CO2 7.000E+12 0.000 0.00 CH2*+CO2 = CH2O+CO 1.400E+13 0.000 0.00 ! ! Reactions of CH2O ! CH2O+H(+M) = CH2OH(+M) 5.400E+11 0.454 3600.00 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/ CH2O+H(+M) = CH3O(+M) 5.400E+11 0.454 2600.00 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/ CH2O+H = HCO+H2 2.300E+10 1.050 3275.00 CH2O+O = HCO+OH 3.900E+13 0.000 3540.00 CH2O+OH = HCO+H2O 3.430E+09 1.180 -447.00 CH2O+O2 = HCO+HO2 1.000E+14 0.000 40000.00 CH2O+HO2 = HCO+H2O2 1.000E+12 0.000 8000.00 CH2O+CH = CH2CO+H 9.460E+13 0.000 -515.00 ! ! Reactions of CH3 ! CH3+H(+M) = CH4(+M) 1.270E+16 -0.630 383.00 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/ CH3+O = CH2O+H 8.430E+13 0.000 0.00 CH3+OH(+M) = CH3OH(+M) 6.300E+13 0.000 0.00 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/ CH3+OH = CH2+H2O 5.600E+07 1.600 5420.00 CH3+OH = CH2*+H2O 2.501E+13 0.000 0.00 ! GRI-Mech 1.2a CH3+O2 = O+CH3O 3.083E+13 0.000 28800.00 CH3+O2 = OH+CH2O 3.600E+10 0.000 8940.00 CH3+HO2 = CH4+O2 1.000E+12 0.000 0.00 ! GRI-Mech 1.2a CH3+HO2 = CH3O+OH 1.340E+13 0.000 0.00 CH3+H2O2 = CH4+HO2 2.450E+04 2.470 5180.00 CH3+C = C2H2+H 5.000E+13 0.000 0.00 CH3+CH = C2H3+H 3.000E+13 0.000 0.00 CH3+HCO = CH4+CO 2.648E+13 0.000 0.00 CH3+CH2O = CH4+HCO 3.320E+03 2.810 5860.00 CH3+CH2 = C2H4+H 4.000E+13 0.000 0.00 CH3+CH2* = C2H4+H 1.200E+13 0.000 -570.00 CH3+CH3(+M) = C2H6(+M) 2.120E+16 -0.970 620.00 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/ CH3+CH3 = H+C2H5 4.990E+12 0.100 10600.00 ! ! Reactions of CH3O/CH2OH ! CH3O+H(+M) = CH3OH(+M) 5.000E+13 0.000 0.00 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/ CH3O+H = CH2OH+H 3.400E+06 1.600 0.00 CH3O+H = CH2O+H2 2.000E+13 0.000 0.00 CH3O+H = CH3+OH 3.200E+13 0.000 0.00 CH3O+H = CH2*+H2O 1.600E+13 0.000 0.00 CH3O+O = CH2O+OH 1.000E+13 0.000 0.00 CH3O+OH = CH2O+H2O 5.000E+12 0.000 0.00 CH3O+O2 = CH2O+HO2 4.280E-13 7.600 -3530.00 ! CH2OH+H(+M) = CH3OH(+M) 1.800E+13 0.000 0.00 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/ CH2OH+H = CH2O+H2 2.000E+13 0.000 0.00 CH2OH+H = CH3+OH 1.200E+13 0.000 0.00 CH2OH+H = CH2*+H2O 6.000E+12 0.000 0.00 CH2OH+O = CH2O+OH 1.000E+13 0.000 0.00 CH2OH+OH = CH2O+H2O 5.000E+12 0.000 0.00 CH2OH+O2 = CH2O+HO2 1.800E+13 0.000 900.00 ! ! Reactions of CH4 ! CH4+H = CH3+H2 6.600E+08 1.620 10840.00 CH4+O = CH3+OH 1.020E+09 1.500 8600.00 CH4+OH = CH3+H2O 1.000E+08 1.600 3120.00 CH4+CH = C2H4+H 6.000E+13 0.000 0.00 CH4+CH2 = CH3+CH3 2.460E+06 2.000 8270.00 CH4+CH2* = CH3+CH3 1.600E+13 0.000 -570.00 ! ! Reactions of CH3OH ! CH3OH+H = CH2OH+H2 1.700E+07 2.100 4870.00 CH3OH+H = CH3O+H2 4.200E+06 2.100 4870.00 CH3OH+O = CH2OH+OH 3.880E+05 2.500 3100.00 CH3OH+O = CH3O+OH 1.300E+05 2.500 5000.00 CH3OH+OH = CH2OH+H2O 1.440E+06 2.000 -840.00 CH3OH+OH = CH3O+H2O 6.300E+06 2.000 1500.00 CH3OH+CH3 = CH2OH+CH4 3.000E+07 1.500 9940.00 CH3OH+CH3 = CH3O+CH4 1.000E+07 1.500 9940.00 ! ! Reactions of C2H ! C2H+H(+M) = C2H2(+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/ C2H+O = CH+CO 5.000E+13 0.000 0.00 C2H+OH = H+HCCO 2.000E+13 0.000 0.00 C2H+O2 = HCO+CO 5.000E+13 0.000 1500.00 ! ! Changed from GRI-MECH v1.2 ! The rate coefficients of the following reaction updated, see notes ! C2H+H2 = H+C2H2 4.900E+05 2.500 560.00 ! ! Reactions of HCCO ! HCCO+H = CH2*+CO 1.000E+14 0.000 0.00 HCCO+O = H+CO+CO 1.000E+14 0.000 0.00 HCCO+O2 = OH+2CO 1.600E+12 0.000 854.00 HCCO+CH = C2H2+CO 5.000E+13 0.000 0.00 HCCO+CH2 = C2H3+CO 3.000E+13 0.000 0.00 HCCO+HCCO = C2H2+CO+CO 1.000E+13 0.000 0.00 ! ! Reactions of C2H2 ! C2H2+H(+M) = C2H3(+M) 5.600E+12 0.000 2400.00 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+O = HCCO+H 1.020E+07 2.000 1900.00 C2H2+O = C2H+OH 4.600E+19 -1.410 28950.00 C2H2+O = CH2+CO 1.020E+07 2.000 1900.00 C2H2+OH = CH2CO+H 2.180E-04 4.500 -1000.00 C2H2+OH = HCCOH+H 5.040E+05 2.300 13500.00 C2H2+OH = C2H+H2O 3.370E+07 2.000 14000.00 C2H2+OH = CH3+CO 4.830E-04 4.000 -2000.00 ! ! Reactions of CH2CO/HCCOH ! CH2CO+H = HCCO+H2 5.000E+13 0.000 8000.00 CH2CO+H = CH3+CO 1.130E+13 0.000 3428.00 CH2CO+O = HCCO+OH 1.000E+13 0.000 8000.00 CH2CO+O = CH2+CO2 1.750E+12 0.000 1350.00 CH2CO+OH = HCCO+H2O 7.500E+12 0.000 2000.00 ! HCCOH+H = CH2CO+H 1.000E+13 0.000 0.00 ! ! Reactions of C2H3 ! C2H3+H(+M) = C2H4(+M) 6.080E+12 0.270 280.00 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/ ! ! Changed to Tsang's recommendation to lower c2h4 flame speed ! C2H3+H = C2H2+H2 6.000E+13 0.000 0.00 ! ! Changed to Tsang's recommendation to lower C2H4 flame speed ! C2H3+O = CH2CO+H 6.000E+13 0.000 0.00 C2H3+OH = C2H2+H2O 5.000E+12 0.000 0.00 ! ! Change from GRI-MECH v 1.2 ! Replace Gutman's k with those of Bozelli and Dean ! C2H3+O2 = C2H2+HO2 1.00E+11 0.0 0.0 ! Est. based on Bozzelli and Dean C2H3+O2 = C2H3O+O 1.24E+13 -0.120 1696.0 ! 760 t C2H3+O2 = HCO+CH2O 8.60E+21 -2.970 3320.0 ! 760 t ! ! Reactions of C2H4 ! C2H4(+M) = H2+C2H2(+M) 8.000E+12 0.440 88770.00 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/ C2H4+H(+M) = C2H5(+M) 1.080E+12 0.454 1820.00 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/ C2H4+H = C2H3+H2 1.325E+06 2.530 12240.00 C2H4+O = CH3+HCO 1.920E+07 1.830 220.00 ! ! lowered by a factor of 2 to lower C2H4 flame speeds ! C2H4+OH = C2H3+H2O 1.800E+06 2.000 2500.00 C2H4+CH3 = C2H3+CH4 2.270E+05 2.000 9200.00 ! ! Reactions of C2H5 ! C2H5+H(+M) = C2H6(+M) 5.210E+17 -0.990 1580.00 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/ C2H5+H = C2H4+H2 2.000E+12 0.000 0.00 C2H5+O = CH3+CH2O 1.320E+14 0.000 0.00 ! ! Replaced by Bozzelli ! C2H5+O2 = HO2+C2H4 3.00E+20 -2.86 6761.0 ! Bozzelli, 1atm ! ! Additional C2H5 reactions from Tsang ! C2H5+HO2 = C2H6+O2 3.00E+11 0.00 0.0 ! TS1 C2H5+HO2 = C2H4+H2O2 3.00E+11 0.00 0.0 ! TS1 C2H5+HO2 = CH3+CH2O+OH 2.40E+13 0.00 0.0 ! TS1 C2H5+H2O2 = C2H6+HO2 8.70E+09 0.00 974.0 ! TS1 C2H5+HCO = C2H6+CO 1.20E+14 0.00 0.0 ! TS1 ! ! Reactions of C2H6 ! C2H6+H = C2H5+H2 1.150E+08 1.900 7530.00 C2H6+O = C2H5+OH 8.980E+07 1.920 5690.00 C2H6+OH = C2H5+H2O 3.540E+06 2.120 870.00 C2H6+CH2* = C2H5+CH3 4.000E+13 0.000 -550.00 C2H6+CH3 = C2H5+CH4 6.140E+06 1.740 10450.00 ! !=========================================================================! ! ! ! C3-up chemistry from the present work - June 1994 ! ! ! !=========================================================================! ! ! C2O taken from Miller-Melius ! HCCO + OH = C2O + H2O 3.00E+13 0.0 0.0 C2O + H = CH + CO 5.00E+13 0.0 0.0 C2O + O = CO + CO 5.00E+13 0.0 0.0 C2O + OH = CO + CO + H 2.00E+13 0.0 0.0 C2O + O2 = CO + CO + O 2.00E+13 0.0 0.0 ! ! C2H3O chemistry ! C2H3O = CH2CO + H 3.95E+38 -7.649 45115. ! Marinov C2H3O + H = CH2CO + H2 3.00E+13 0.0 0.0 ! Estimated C2H3O + O = CH2O + HCO 1.00E+14 0.0 0.0 ! Marinov C2H3O + O = CH2CO + OH 1.00E+13 0.0 0.0 ! Estimated C2H3O + OH = CH2CO + H2O 5.00E+12 0.0 0.0 ! Estimated C2H3O + O2 = CH2CO + HO2 1.40E+11 0.0 0.0 ! CEC C2H3O + O2 = CH2O + CO + OH 1.80E+10 0.0 0.0 ! CEC C2H3O + CH3 = C2H5 + HCO 4.90E+14 -0.50 0.0 ! marinov ! CH3 + HCCO = C2H4 + CO 5.00E+13 0.0 0.0 ! Estimated CH3 + C2H = C3H3 + H 2.41E+13 0.0 0.0 ! Tsang-Hampson CH4 + C2H = C2H2 + CH3 1.81E+12 0.0 500.0 ! 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 + 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 C2H2 + HCCO = C3H3 + CO 1.00E+11 0.0 3000.0 ! Miller-Bowman C2H4 + O2 = C2H3 + HO2 4.22E+13 0.0 60800.0 ! Tsang-Hampson +3.2 kcal/mol C2H3 + H2O2 = C2H4 + HO2 1.21E+10 0.0 -596.0 ! Tsang-Hampson C2H3 + HCO = C2H4 + CO 9.00E+13 0.0 0.0 ! Tsang-Hampson C2H3 + CH3 = C2H2 + CH4 3.92E+11 0.0 0.0 ! Tsang-Hampson 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 + O = C2H2 + CO 6.80E+13 0.0 0.0 ! Warnatz 82 C3H2 + OH = HCO + C2H2 6.80E+13 0.0 0.0 ! Warnatz 82 C3H2 + O2 = HCCO + CO + H 5.00E+13 0.0 0.0 ! Miller-Melius 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 ! ! These rate coefficients may need work. ! C3H3 + H (+M) = aC3H4 (+M) 3.00E+13 0.0 0.0 ! Est. See notes LOW/ 1.4E+31 -5.00 -6000.0/ TROE / 0.5 2000. 10.0 10000.0/ H2/2.0/ H2O/6.0/ CH4/2.0/ CO/1.5/ CO2/2.0/ C2H6/3.0/ AR/0.7/ C3H3 + H (+M) = pC3H4 (+M) 3.00E+13 0.0 0.0 ! Est. See notes LOW/ 1.4E+31 -5.00 -6000.0/ TROE / 0.5 2000. 10.0 10000.0/ H2/2.0/ H2O/6.0/ CH4/2.0/ CO/1.5/ CO2/2.0/ C2H6/3.0/ AR/0.7/ C3H3 + O = CH2O + C2H 2.00E+13 0.0 0.0 ! Miller-Bowman ! ! Products reassigned to avoid C3H3 and C3H2 build-up ! C3H3 + OH = C3H2 + H2O 2.00E+13 0.0 0.0 ! Miller-Bowman C3H3 + OH = C2H3 + HCO 4.00E+13 0.0 0.0 ! Estimated C3H3 + O2 = CH2CO + HCO 3.00E+10 0.0 2868.0 ! Gutman C3H3 + HO2 = aC3H4 + O2 1.00E+11 0.0 0.0 ! Estimated * C3H3 + HO2 = pC3H4 + O2 1.00E+11 0.0 0.0 ! Estimated * 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 + 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+13 0.0 0.0 ! kinf assumed falloff=C2H3+CH3 TS1 600 cm-1 LOW /2.60E+58 -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/ ! aC3H4 + H = C3H3 + H2 1.30E+06 2.0 5500.0 ! = pC3H4 + H aC3H4 + O = CH2CO + CH2 2.00E+07 1.8 1000.0 ! Est. See notes aC3H4 + OH = C3H3 + H2O 5.30E+06 2.0 2000.0 ! Refit to Liu(note aC3H4 + CH3 = iC4H7 2.00E+11 0.00 7500.0 ! PW P aC3H4 + C2H = C2H2 + C3H3 1.00E+13 0.0 0.0 ! Estimated/ ! ! Because aC3H4 to pC3H4 isomerization proceeds with cyclopropene as an ! intermediate, most literature data represent the global kinetics of ! the isomerization process. Such an isomerization does not ! need to obey detailed balancing, if the experimental rate coefficients are ! used. The rate coefficients below are best fits to available experimental ! data (need to incorporate pressure dependence in the future). As the first ! step, we use only the rate coefficient of pC3H4 -> aC3H4, and assume it to ! be reversible ! aC3H4 => pC3H4 5.40E+13 0.0 65000.0 ! Fit ! duplicate pC3H4 => aC3H4 1.40E+13 0.0 64400.0 ! Fit ! duplicate ! ! or just take Melius kinf ! ! pC3H4 + H = C3H3 + H2 1.30E+06 2.0 5500.0 ! Estimated (from Wu and Kern) ! ! Replace Dean and Westmoreland's (DW) QRRK rate coefficient by that of Hidaka. ! DW's anaylsis seems to yield too large a rate coefficient for pC3H4 + H ! pC3H4 + H = CH3 + C2H2 1.30E+05 2.5 1000.0 ! Hidaka pC3H4 + O = HCCO + CH3 1.73E+13 0.0 2250.0 ! Fontijn pC3H4 + O = C3H3 + OH 3.45e+04 2.16 4830.0 ! Fontijn pC3H4 + OH = C3H3 + H2O 1.00E+06 2.0 100.0 ! This work pC3H4 + C2H = C2H2 + C3H3 1.00E+13 0.0 0.0 ! Estimated ! ! Reactions of C4H and C4H2 ! 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/ ! C4H + O = C2H + C2O 5.00E+13 0.0 0.0 ! = C2H + O C4H + O2 = HCCO + C2O 5.00E+13 0.0 1500.0 ! = C2H + O2 C4H + H2 = H + C4H2 4.90E+05 2.5 560.0 ! = C2H + H2 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? C4H2 + OH = C4H + H2O 3.37E+07 2.0 14000.0 ! = C2H2 + OH 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 H2C4O + O = CH2CO + C2O 2.00E+07 1.9 200.0 ! Estimated ! ! 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 + C2H3O 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+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 + 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 ! ! Reactions up to benzene formation and oxidation ! ! C4H + C2H2 = C6H2 + H 9.60E+13 0.0 0.0 ! = C2H2 + C2H C4H2 + CH = C5H2 + H 5.00E+13 0.0 0.0 ! Estimated C4H2 + CH2 = C5H3 + H 1.30E+13 0.0 4300.0 ! = C2H2 + CH2 C4H2 + CH2* = C5H3 + H 5.00E+13 0.0 0.0 ! Miller-Melius 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 2.00E+12 0.0 0.0 ! Estimated, 760 t n-C4H3 + C2H2 = l-C6H4 + H 2.5E+14 -0.56 10600. ! 760 t n-C4H3 + C2H2 = n-C6H5 2.7E+36 -7.62 16200. ! 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 C4H4 + C2H3 = l-C6H6 + H 2.8E+21 -2.44 14720.0 ! 760 t n-C4H5 + C2H2 = n-C6H7 1.1E+14 -1.27 2900. ! 760 t n-C4H5 + C2H2 = c-C6H7 5.0E+24 -5.46 4600. ! 760 t n-C4H5 + C2H2 = l-C6H6 + H 5.8E+08 1.02 10900. ! 760 t n-C4H5 + C2H2 = A1 + H 1.6E+16 -1.33 5400. ! 760 t C4H6 + C2H3 = C6H8 + H 2.8E+21 -2.44 14720.0 ! 760 t ! ! ! Reactions of C5H2 and C5H3 ! C5H2 + OH => C4H2 + H + CO 2.00E+13 0.0 0.0 ! Estimated C5H2 + CH = C6H2 + H 5.00E+13 0.0 0.0 ! Estimated C5H2 + O2 = H2C4O + CO 1.00E+12 0.0 0.0 ! Estimated C5H3 + OH = C5H2 + H2O 1.00E+13 0.0 0.0 ! Estimated C5H3 + CH = C6H2 + H + H 5.00E+13 0.0 0.0 ! Estimated C5H3 + CH2 = l-C6H4 + H 5.00E+13 0.0 0.0 ! = C3H3+CH2 C5H3 + O2 = H2C4O + HCO 1.00E+12 0.0 0.0 ! Estimated ! ! Reactions of C6H and C6H2 ! C6H + H (+M) = C6H2 (+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/ C6H2 + H = C6H3 1.10E+30 -4.92 10800.0 ! RRKM, 760 t C6H + O = C4H + C2O 5.00E+13 0.0 0.0 ! = C2H + O C6H + H2 = H + C6H2 4.90E+05 2.5 560.0 ! = C2H + H2 C6H2 + O = C5H2 + CO 2.70E+13 0.0 1720.0 ! = C4H2 + O C6H2 + OH =>C2H+C2H2+C2O 6.60E+12 0.0 -410.0 ! = C4H2 + OH C6H2 + OH = C6H + H2O 3.37E+07 2.0 14000.0 ! = C2H2 + OH ! ! 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 = n-C6H5 5.9E+39 -8.25 15600. ! 760 t 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 C6H5 and C6H6 ! n-C6H5 = A1- 5.1E+54 -13.11 35700. ! 760 t n-C6H5 = c-C6H4 + H 1.3E+59 -13.56 62000. ! 760 t n-C6H5 + H = i-C6H5 + H 2.50E+20 -1.67 10800.0 ! RRKM, 760 t n-C6H5 + H = C4H4 + C2H2 6.30E+25 -3.34 10014.0 ! RRKM, 760 t i-C6H5 + H = C4H4 + C2H2 2.80E+23 -2.55 10780.0 ! RRKM, 760 t n-C6H5 + H = l-C6H6 2.00E+47 -10.26 13070.0 ! RRKM, 760 t i-C6H5 + H = l-C6H6 3.40E+43 -9.01 12120.0 ! RRKM, 760 t n-C6H5 + H = l-C6H4 + H2 1.50E+13 0.00 0.0 ! 0.5*C2H3+H i-C6H5 + H = l-C6H4 + H2 3.00E+13 0.00 0.0 ! C2H3+H n-C6H5 + OH = l-C6H4 + H2O 2.00E+12 0.00 0.0 i-C6H5 + OH = l-C6H4 + H2O 4.00E+12 0.00 0.0 n-C6H5 + O2 => C4H4 + CO + HCO 4.16E+10 0.00 2500. ! =(n-C4H5+O2) i-C6H5 + O2 => CH2CO+CH2CO+C2H 7.86E+16 -1.80 0.0 ! =(i-C4H3+O2) l-C6H6 + H = n-C6H7 1.5E+16 -1.69 1600. ! 760 t l-C6H6 + H = c-C6H7 4.7E+27 -6.11 3800. ! 760 t l-C6H6 + H = A1 + H 2.0E+18 -1.73 4500. ! 760 t l-C6H6 + H = n-C6H5 + H2 6.65E+05 2.53 12240.0 ! = C2H4 + H/2 l-C6H6 + H = i-C6H5 + H2 3.33E+05 2.53 9240.0 ! -3kcal/mol,/4 l-C6H6 + OH = n-C6H5 + H2O 6.20E+06 2.0 3430.0 ! see notes l-C6H6 + OH = i-C6H5 + H2O 3.10E+06 2.0 430.0 ! see notes ! ! Reactions of C6H7 and C6H8 ! n-C6H7 = c-C6H7 1.2E+31 -7.95 8900. ! 760 t n-C6H7 = A1 + H 3.2E+26 -4.99 15500. ! 760 t n-C6H7 + H = i-C6H7 + H 2.4E+49 -10.72 15100. ! 760 t i-C6H7 + H = C6H8 1.8E+39 -7.62 11000. ! 760 t n-C6H7 + H = C6H8 5.6E+48 -10.54 14700. ! 760 t n-C6H7 + H = l-C6H6 + H2 1.5E+13 0.00 0. i-C6H7 + H = l-C6H6 + H2 3.0E+13 0.00 0. n-C6H7 + OH = l-C6H6 + H2O 2.0E+12 0.00 0. i-C6H7 + OH = l-C6H6 + H2O 4.0E+12 0.00 0. n-C6H7 + O2 => C4H6 + CO + HCO 4.16E+10 0.00 2500. ! =(n-C4H5+O2) i-C6H7 + O2 => CH2CO+CH2CO+C2H3 7.86E+16 -1.80 0.0 ! =(i-C4H3+O2) ! C6H8 + H = n-C6H7 + H2 1.33E+06 2.53 12240.0 ! = C2H4 + H C6H8 + H = i-C6H7 + H2 6.65E+05 2.53 9240.0 ! -3kcal/mol, /2 C6H8 + OH = n-C6H7 + H2O 6.20E+06 2.0 3430.0 ! see notes C6H8 + OH = i-C6H7 + H2O 3.10E+06 2.0 430.0 ! see notes ! ! Reactions of benzene and phenyl ! A1 + H = c-C6H7 2.0E+38 -8.32 6400. ! 760 t 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 2.10E+12 0.0 7470.0 ! LIN ! C6H5O = CO + C5H5 2.50E+11 0.0 43900.0 ! LIN 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. ! 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 = C5H6 1.00E+14 0.0 0.0 ! Brezinsky 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 ! ! Butane and propane chemistry ! ! ! Reactions of n-butane ! C4H10+H = pC4H9+H2 9.20E+05 2.54 6756.0 ! =(C3H8+H scaled to BBW at 753K) C4H10+H = sC4H9+H2 2.40E+06 2.40 4471.0 ! =(C3H8+H scaled to BBW at 753K) C4H10+O = pC4H9+OH 4.90E+06 2.40 5500.0 ! CW C4H10+O = sC4H9+OH 4.30E+05 2.60 2580.0 ! CW C4H10+OH = pC4H9+H2O 3.30E+07 1.80 954.0 ! C C4H10+OH = sC4H9+H2O 5.40E+06 2.00 -596.0 ! C C4H10+O2 = pC4H9+HO2 4.00E+13 0.00 50930.0 ! =(C3H8+O2) TS3 C4H10+O2 = sC4H9+HO2 8.00E+13 0.00 47590.0 ! =(C3H8+O2)*2 TS3 C4H10+HO2 = pC4H9+H2O2 4.76E+04 2.55 16490.0 ! =(C3H8+HO2) TS3 C4H10+HO2 = sC4H9+H2O2 1.90E+04 2.60 13910.0 ! =(C3H8+HO2)*2 TS3 C4H10+CH3 = pC4H9+CH4 9.03E-01 3.65 7153.0 ! =(C3H8+CH3) TS3 see notes C4H10+CH3 = sC4H9+CH4 3.00E+00 3.46 5480.0 ! =(C3H8+CH3)*2 TS3 see notes ! ! Reactions of i-butane ! iC4H10+H = iC4H9+H2 1.80E+06 2.54 6760.0 ! TS4 iC4H10+H = tC4H9+H2 6.00E+05 2.40 2580.0 ! TS4 iC4H10+O = iC4H9+OH 4.30E+05 2.50 3640.0 ! TS4 iC4H10+O = tC4H9+OH 1.57E+05 2.50 1110.0 ! TS4 iC4H10+OH = iC4H9+H2O 2.30E+08 1.53 775.0 ! TS4 iC4H10+OH = tC4H9+H2O 5.73E+10 0.51 64.0 ! TS4 iC4H10+HO2 = iC4H9+H2O2 3.00E+04 2.55 15500.0 ! TS4 iC4H10+HO2 = tC4H9+H2O2 3.60E+03 2.55 10500.0 ! TS4 iC4H10+O2 = iC4H9+HO2 4.00E+13 0.00 50900.0 ! TS4 iC4H10+O2 = tC4H9+HO2 4.00E+13 0.00 44000.0 ! TS4 iC4H10+CH3 = iC4H9+CH4 1.36E+00 3.65 7150.0 ! TS4 iC4H10+CH3 = tC4H9+CH4 9.00E-01 3.46 4600.0 ! TS4 ! ! Reactions of 1-butyl ! pC4H9+H(+M) = C4H10(+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/ ! pC4H9+H = C2H5+C2H5 3.70E+24 -2.92 12505.0 ! =(nC3H7+H) TS3 1 atm ! pC4H9+H = C4H81+H2 1.80E+12 0.00 0.0 ! =(nC3H7+H) TS4 pC4H9+O = nC3H7+CH2O 9.60E+13 0.00 0.0 ! =(nC3H7+O) TS3 ka+kb pC4H9+OH = C4H81+H2O 2.40E+13 0.00 0.0 ! =(nC3H7+OH) TS3 pC4H9+O2 = C4H81+HO2 2.70E+11 0.00 0.0 ! BB75 pC4H9+HO2 = nC3H7+OH+CH2O 2.40E+13 0.00 0.0 ! =(nC3H7+HO2) TS3 ? pC4H9+HCO = C4H10+CO 9.00E+13 0.00 0.0 ! =(nC3H7+HCO) TS3 pC4H9+CH3 = C4H81+CH4 1.10E+13 0.00 0.0 ! =(nC3H7+CH3) TS3 ! ! Reactions of 2-butyl ! sC4H9+H(+M) = C4H10(+M) 2.40E+13 0.00 0.0 ! =(iC3H7+H) 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/ sC4H9+H = C2H5+C2H5 1.40E+28 -3.94 15916.0 ! =(iC3H7+H) TS3 1 atm ! sC4H9+H = C4H81+H2 3.20E+12 0.00 0.0 ! =(iC3H7+H) TS3 sC4H9+H = C4H82+H2 2.10E+12 0.00 0.0 ! =(iC3H7+H)*2/3 TS3 sC4H9+O = CH3CHO+C2H5 9.60E+13 0.00 0.0 ! =(iC3H7+O) TS3 ka+kb sC4H9+OH = C4H81+H2O 2.40E+13 0.00 0.0 ! =(iC3H7+OH) TS3 sC4H9+OH = C4H82+H2O 1.60E+13 0.00 0.0 ! =(iC3H7+OH)*2/3 TS3 sC4H9+O2 = C4H81+HO2 5.10E+10 0.00 0.0 ! BB75 sC4H9+O2 = C4H82+HO2 1.20E+11 0.00 0.0 ! BB75 sC4H9+HO2 = CH3CHO+C2H5+OH 2.40E+13 0.00 0.0 ! =(iC3H7+HO2) TS3 ? sC4H9+HCO = C4H10+CO 1.20E+14 0.00 0.0 ! =(iC3H7+HCO) TS3 sC4H9+CH3 = CH4+C4H81 2.20E+14 -0.68 0.0 ! =(iC3H7+CH3) TS3 sC4H9+CH3 = CH4+C4H82 1.50E+14 -0.68 0.0 ! =(iC3H7+CH3)*2/3 TS3 ! ! Reactions of i-butyl ! iC4H9+H(+M) = iC4H10(+M) 3.60E+13 0.00 0.0 ! TS4, 600cm-1 LOW / 3.27E+56 -11.74 6430.8 / TROE / 0.506 1266.6 1266.6 50000.0 / H2/2/ H2O/6/ CH4/2/ CO/1.5/ CO2/2/ C2H6/3/ AR/0.7/ ! !iC4H9+H = iC3H7+CH3 1.10E+32 -5.04 16760.0 ! TS4 eq 0.1 atm iC4H9+H = iC3H7+CH3 1.90E+35 -5.83 22470.0 ! TS4 eq 1 atm ! iC4H9+H = iC4H8+H2 9.00E+11 0.00 0.0 ! TS4 iC4H9+O = iC3H7+CH2O 9.60E+13 0.00 0.0 ! TS4 iC4H9+OH = iC4H8+H2O 1.20E+13 0.00 0.0 ! TS4 iC4H9+O2 = iC4H8+HO2 2.40E+10 0.00 0.0 ! TS4 iC4H9+HO2 = iC3H7+CH2O+OH 2.41E+13 0.00 0.0 ! TS4 ? iC4H9+HCO = iC4H10+CO 3.60E+13 0.00 0.0 ! TS4 iC4H9+CH3 = iC4H8+CH4 6.00E+12 -0.32 0.0 ! TS4 ! ! Reactions of t-butyl ! tC4H9(+M) = iC4H8+H(+M) 8.30E+13 0.00 38150.4 ! TS4 600cm-1 LOW / 1.90E+41 -7.36 36631.7 / TROE / 0.293 649.0 60000.0 3425.9 / H2/2/ H2O/6/ CH4/2/ CO/1.5/ CO2/2/ C2H6/3/ AR/0.7/ tC4H9+H(+M) = iC4H10(+M) 2.40E+13 0.00 0.0 ! TS4, 600cm-1 LOW / 1.47E+61 -12.94 8000.0 / TROE / 0.000 1456.4 1000.0 10000.5 / H2/2/ H2O/6/ CH4/2/ CO/1.5/ CO2/2/ C2H6/3/ AR/0.7/ ! tC4H9+H = iC3H7+CH3 2.60E+36 -6.12 25640.0 ! TS4 eq 1 atm ! tC4H9+H = iC4H8+H2 5.42E+12 0.00 0.0 ! TS4 tC4H9+O = iC4H8+OH 1.80E+14 0.00 0.0 ! TS4 tC4H9+O = CH3COCH3+CH3 1.80E+14 0.00 0.0 ! TS4 tC4H9+OH = iC4H8+H2O 1.80E+13 0.00 0.0 ! TS4 tC4H9+O2 = iC4H8+HO2 4.80E+11 0.00 0.0 ! TS4 tC4H9+HO2 = CH3+CH3COCH3+OH 1.80E+13 0.00 0.0 ! TS4 tC4H9+HCO = iC4H10+CO 6.00E+13 0.00 0.0 ! TS4 tC4H9+CH3 = iC4H8+CH4 3.80E+15 -1.00 0.0 ! TS4 ! CH3COCH3+H = H2+CH2CO+CH3 1.30E+06 2.54 6756.0 ! =C3H8+H CH3COCH3+O = OH+CH2CO+CH3 1.90E+05 2.68 3716.0 ! =C3H8+O CH3COCH3+OH = H2O+CH2CO+CH3 1.40E+03 2.66 527.0 ! =C3H8+OH CH3+CH3CO = CH3COCH3 4.00E+15 -0.80 0.0 ! TS1 kinf ! ! Reactions of 1-butene ! C4H81+H(+M) = pC4H9(+M) 1.33E+13 0.00 3260.7 ! =(C3H6+H) 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/ C4H81+H(+M) = sC4H9(+M) 1.33E+13 0.00 1559.8 ! =(C3H6+H) TS5 600 cm-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/ C4H81+H = C2H4+C2H5 8.00E+21 -2.39 11180.0 ! =(C3H6+H) TS5 1 atm ! 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 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 2-butene ! C4H82+H(+M) = sC4H9(+M) 1.33E+13 0.00 1559.8 ! =(C3H6+H=iC3H7) 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/ ! C4H82+H = C4H7+H2 3.40E+05 2.50 2490.0 ! =(C3H6+H)*2 TS5 k(a) C4H82+O = C2H4+CH3CHO 2.40E+08 1.65 327.0 ! =(C3H6+O)*2 TS5 k(a+b) C4H82+OH = C4H7+H2O 6.20E+06 2.00 -298.0 ! =(C3H6+OH)*2 TS5 C4H82+O2 = C4H7+HO2 5.00E+13 0.00 53300.0 ! Estimated C4H82+HO2 = C4H7+H2O2 1.90E+04 2.60 13910.0 ! =(C3H6+HO2)*2 TS5 C4H82+CH3 = C4H7+CH4 4.40E+00 3.50 5675.0 ! =(C3H6+CH3)*2 TS5 k(c) ! ! Reactions of i-butene ! iC4H8+H(+M) = iC4H9(+M) 1.33E+13 0.00 3260.7 ! =(C3H6+H=nC3H7) 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/ iC4H8+H = iC4H7+H2 1.20E+06 2.54 6760.0 ! =(iC4H10+H)*2/3 TS4 ! iC4H8+H = C3H6+CH3 8.00E+21 -2.39 11180.0 ! =(iC4H8+H) TS5 1 atm ! iC4H8+O = CH3+CH3+CH2CO 1.20E+08 1.65 327.0 ! =(C3H6+O) TS5 iC4H8+O = iC3H7+HCO 3.50E+07 1.65 -972.0 ! =(C3H6+O) TS5 k(c) iC4H8+O = iC4H7+OH 2.90E+05 2.50 3640.0 ! =(iC4H10+O)*2/3 TS4 iC4H8+OH = iC4H7+H2O 1.50E+08 1.53 775.0 ! =(iC4H10+OH)*2/3 TS4 iC4H8+HO2 = iC4H7+H2O2 2.00E+04 2.55 15500.0 ! =(iC4H10+HO2)*2/3 TS4 iC4H8+O2 = iC4H7+HO2 2.70E+13 0.00 50900.0 ! =(iC4H10+O2)*2/3 TS4 iC4H8+CH3 = iC4H7+CH4 9.10E-01 3.65 7150.0 ! =(iC4H10+CH3)*2/3 TS4 ! ! 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+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 2-methylpropen-3-yl ! iC4H7+H(+M) = iC4H8(+M) 2.00E+14 0.00 0.0 ! =(aC3H5+H) TS5 600cm-1 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/ iC4H7+H = sC3H5+CH3 2.60E+45 -8.19 37890.0 ! =(aC3H5+H) TS5 1 atm iC4H7+O = CH2O+sC3H5 9.00E+13 0.00 0.0 ! Estimated iC4H7+HO2 = sC3H5+CH2O+OH 4.00E+12 0.00 0.0 ! Estimated ! ! Reactions of propane ! 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 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/ nC3H7+H = C2H5+CH3 3.70E+24 -2.92 12505.0 ! TS3 1 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 ! ! kinf : TS3 recommendation ! ko: scaled such that Pr(nC3H7+CH3) = Pr(C2H5+CH3) 500cm-1 ! Fc: assumed equal to Fc(C2H5+CH3) ! nC3H7+CH3(+M) = C4H10(+M) 1.93E+14 -0.32 0.0 ! LOW / 2.68E+61 -13.24 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/ ! ! 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 1.40E+28 -3.94 15916.0 ! TS3 1 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(+M) = iC4H10(+M) 1.40E+15 -0.68 0.0 ! TS4, 600cm-1 LOW / 4.16E+61 -13.33 3903.4 / TROE / 0.931 60000.0 1265.3 5469.8 / H2/2/ H2O/6/ CH4/2/ CO/1.5/ CO2/2/ C2H6/3/ AR/0.7/ 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/ 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 8.00E+21 -2.39 11180.0 ! TS5 1 atm ! C3H6+H = aC3H5+H2 1.70E+05 2.50 2490.0 ! TS5 k(a) C3H6+H = sC3H5+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 = aC3H5+OH 1.80E+11 0.70 5880.0 ! TS5 k(d) C3H6+O = sC3H5+OH 6.00E+10 0.70 7630.0 ! TS5 K(f) C3H6+OH = aC3H5+H2O 3.10E+06 2.00 -298.0 ! TS5 C3H6+OH = sC3H5+H2O 1.10E+06 2.00 1450.0 ! TS5 C3H6+HO2 = aC3H5+H2O2 9.60E+03 2.60 13910.0 ! TS5 C3H6+CH3(+M) = sC4H9(+M) 1.70E+11 0.00 7403.6 ! TS5 600cm-1 LOW / 2.31E+28 -4.27 1831.0 / TROE / 0.565 60000.0 534.2 3007.2 / H2/2/ H2O/6/ CH4/2/ CO/1.5/ CO2/2/ C2H6/3/ AR/0.7/ C3H6+CH3(+M) = iC4H9(+M) 9.60E+10 0.00 8003.6 ! TS5 600cm-1 LOW / 1.30E+28 -4.27 2431.1 / TROE / 0.565 60000.0 534.2 3007.2 / H2/2/ H2O/6/ CH4/2/ CO/1.5/ CO2/2/ C2H6/3/ AR/0.7/ C3H6+CH3 = aC3H5+CH4 2.20E+00 3.50 5675.0 ! TS5 k(c) C3H6+CH3 = sC3H5+CH4 8.40E-01 3.50 11660.0 ! TS5 k(e) ! ! Reactions of allyl ! aC3H5+H(+M) = C3H6(+M) 2.00E+14 0.00 0.0 ! TS5 600cm-1 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/ ! aC3H5+H = aC3H4+H2 1.80E+13 0.00 0.0 ! TS5 k(c) aC3H5+O = C2H3CHO+H 6.00E+13 0.00 0.0 ! TS5 aC3H5+OH = C2H3CHO+H+H 4.20E+32 -5.16 30126.0 ! TS5, 1 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 = CH3CO+CH2O 1.19E+15 -1.01 20128.0 ! Bozzelli, 1 atm aC3H5+O2 = C2H3CHO+OH 1.82E+13 -0.41 22859.0 ! Bozzelli, 1 atm ! aC3H5+HO2 = C3H6+O2 2.66E+12 0.00 0.0 ! CEC aC3H5+HO2 = OH+C2H3+CH2O 6.63E+12 0.00 0.0 ! CEC ! aC3H5+HCO = C3H6+CO 6.00E+13 0.00 0.0 ! TS5 ! !aC3H5+CH3(+M) = C4H81(+M) 1.00E+14 -0.32 -262.3 ! TS5 600cm-1 ! LOW / 3.91E+60 -12.81 6250.0 / ! TROE / 0.104 1606.0 60000.0 6118.4 / ! H2/2/ H2O/6/ CH4/2/ CO/1.5/ CO2/2/ C2H6/3/ AR/0.7/ 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 3.00E+12 -0.32 -131.0 ! TS5 k(a) aC3H4+H(+M) = aC3H5(+M) 1.20E+11 0.69 3006.3 ! TW 500 cm-1 LOW / 5.74E+43 -7.67 7000.0 / TROE / 0.237 987.3 60000.0 7028.3 / H2/2/ H2O/6/ CH4/2/ CO/1.5/ CO2/2/ C2H6/3/ AR/0.7/ ! ! Reactions of propen-2-yl ! sC3H5+H = pC3H4+H2 3.34E+12 0.00 0.0 ! PW sC3H5+O = CH3+CH2CO 6.00E+13 0.00 0.0 ! Estimated sC3H5+OH = CH3+CH2CO+H 5.00E+12 0.00 0.0 ! Estimated sC3H5+O2 = CH3+CO+CH2O 4.34E+12 0.00 0.0 ! PW sC3H5+HO2 = CH3+CH2CO+OH 2.00E+13 0.00 0.0 ! Estimated sC3H5+HCO = C3H6+CO 9.00E+13 0.00 0.0 ! Estimated sC3H5+CH3 = pC3H4+CH4 1.00E+11 0.00 0.0 ! PW sC3H5+CH3 = iC4H8 2.00E+13 0.00 0.0 ! PW P ! pC3H4+H = sC3H5 6.50E+12 0.00 2000.0 ! PW P !pC3H4+H = sC3H5 2.00E+13 0.00 2000.0 ! Estimated ! ! Reactions of CH3CHO ! CH3CHO+O2 = CH3CO+HO2 3.00E+13 0.00 39100.0 ! CEC CH3CHO+OH = CH3CO+H2O 2.35E+10 0.73 -1110.0 ! CEC CH3CHO+H = CH3CO+H2 4.10E+09 1.16 2400.0 ! CEC CH3CHO+O = CH3CO+OH 5.80E+12 0.00 1800.0 ! CEC CH3CHO+CH3 = CH3CO+CH4 2.00E-06 5.60 2460.0 ! CEC ! ! Reactions of CH3CO ! CH3CO+M = CH3+CO+M 8.70E+42 -8.62 22420.0 ! TS1 H2/2/ H2O/6/ CH4/2/ CO/1.5/ CO2/2/ C2H6/3/ AR/0.7/ CH3CO+H = CH3+HCO 9.60E+13 0.00 0.0 ! TS1 CH3CO+O = CH2CO+OH 3.90E+13 0.00 0.0 ! CEC CH3CO+O = CH3+CO2 1.50E+14 0.00 0.0 ! CEC CH3CO+OH = CH2CO+H2O 1.20E+13 0.00 0.0 ! TS1 CH3CO+OH = CH3+CO+OH 3.00E+13 0.00 0.0 ! TS1 CH3CO+HO2 = CH3+CO2+OH 3.00E+13 0.00 0.0 ! TS1 CH3CO+H2O2 = CH3CHO+HO2 1.80E+11 0.00 8226.0 ! TS1 ! ! Recombination reactions of C1 and C2 species ! CH3+HCO = CH3CHO 1.80E+13 0.00 0.0 ! TS1 kinf (to be RRKMed) ! CH3+C2H2 = aC3H4+H 6.74E+19 -2.08 31591.0 ! DW 1 atm ! ! CH3+C2H2 = aC3H5 2.61E+46 -9.82 36951.0 ! DW 1 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/ ! CH3+C2H3 = aC3H5+H 1.50E+24 -2.83 18618.0 ! TS1 1 atm ! CH3+C2H4 = nC3H7 3.30E+11 0.00 7700.0 ! KP 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/ ! C2H3+C2H4 = C4H7 7.93E+38 -8.47 14220.0 ! HW 1 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/ C2H3+C2H5 = aC3H5+CH3 3.90E+32 -5.22 19747.0 ! TS1 1 atm ! C2H4+C2H5 = pC4H9 1.50E+11 0.00 7300.0 ! KP, P ! ! 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) ! C2H5+C2H5(+M) = C4H10(+M) 1.88E+14 -0.50 0.0 ! LOW / 2.61E+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/ ! ! ! 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