!MECHANISM C2-O2 system at high-temperature conditions, Ion Chemistry !Cite: J. Prager, U. Riedel, J. Warnatz: Modeling Ion Chemistry and Charged Species Diffusion in Lean Methane-Oxygen Flames, Proceedings of the Combustion Institute, 31, 1129-1137, 2006. !renamed species: !1CH2 => On-CH2,3CH2 => Th-CH2 ! No further distribution ! Only for acadamic/non-commercial use !-------------------------------------------------------------------------------- ELEMENTS C H O N END SPECIES O2 H2 OH H O HO2 H2O H2O2 CO CO2 CH CHO On-CH2 Th-CH2 CH3 CH2O CH4 CH3O CH2OH CH3O2 CH3OH CH3O2H C2H HCCO C2H2 CH2CO C2H3 CH3CO CH2CHO C2H4 CH3CHO C2H5 C2H5O CH3CHOH CH2CH2OH C2H5OH C2H6 C H3O+ CHO+ C2H3O+ CH5O+ O2- OH- E- CO3- CHO2- O- CHO3- AR N2 END REACTIONS KJOULES/MOLE MOLES !****************************************** !**** 01. H2-O2 React. (no HO2, H2O2) !****************************************** !---- CEC 94, (9.756E+13/0/62.10) (300-5000 K, dlog k= +-0.1 rising to +-0.5) !---- k_r, CEC 94, k=(1.2E+13/0/-0.931), (220-500K, dlog k= +-0.2) !---- k=(1.445+13/0/2.935), (1000-2000K, dlog k= +-0.1) O2 +H =OH +O 9.700E+13 0.0 62.100 !---- CEC 94 (5.120E+04/2.67/26.27) (300-2500 K,dlogk = +-0.5 rising to +-0.2) H2 +O =OH +H 5.060E+04 2.670 26.300 !---- CEC 94 (1.000E+08/1.6/13.80) (300-2500 K,dlogk = +-0.1 rising to +-0.3) !---- k_r, CEC 94, k=(4.517+08/1.6/77.071), (300-2500, dlog k= +-0.2) H2 +OH =H2O +H 1.000E+08 1.600 13.800 !---- CEC 94 (1.506E+09/1.14/0.416) (250-2500 K, dlogk = +-0.2) OH +OH =H2O +O 1.500E+09 1.140 0.420 !****************************************** !**** 02. Recombination Reactions !****************************************** !---- OK CEC 94 k(AR)=(6.53e+17/-1.0/0),(300-2500K,dlog k=+-0.5), here given for H2 !---- CEC 94 k(H2)=(9.790E+16/-0.6/0), (100-5000 K, dlogk = +-0.5) H +H (+M) =H2 (+M) 1.800E+18 -1.000 0.000 H2 /1.0 /H2O /6.5 /O2 /0.4 /AR /0.35 /N2 /0.4 /CO /0.75 /CO2 /1.5 /CH4 /3.0 / !---- 86 TSA/HAM k=(5.400E+13 0.000 -7.48) !---- (GIVEN HERE FOR H2,MEASURED FOR AR, 200-4000 K, dlog k = +-1.3)) O +O (+M) =O2 (+M) 5.400E+13 0.000 -7.4 !---- OK CEC 94 (GIVEN FOR H2),MEASURED FOR H2O, AR, N2,(300-3000 K, dlogk=+-0.5) H2 /1.0 /H2O /6.5 /O2 /0.4 /AR /0.35 /N2 /0.4 /CO /0.75 /CO2 /1.5 /CH4 /3.0 / !---- (MEASURED FOR H2O, GIVEN HERE FOR H2) (2.176E+22/-2.0/0.0) !---- (MEASURED FOR AR, GIVEN HERE FOR H2) (2.383E+22/-2.0/0.0) !---- (MEASURED FOR N2, GIVEN HERE FOR H2) (5.531E+22/-2.0/0.0) H +OH (+M) =H2O (+M) 5.530E+22 -2.000 0.000 H2 /1.0 /H2O /2.55 /O2 /0.4 /AR /0.35 /N2 /0.4 /CO /0.75 /CO2 /1.5 /CH4 /3.0 / !****************************************** !**** 03. HO2 Formation/Consumption !****************************************** !---- CEC 94 k=(2.103E+18/-0.8/0), (MEASURED FOR H2), (300-2000K, dlogk = +-0.5) !---- ALSO MEASURED FOR AR AND N2, (300-2000K, dlogk = +-0.5) !---- (MEASURED FOR AR, GIVEN HERE FOR H2) (1.761E+18/-0.8/0.0) !---- (MEASURED FOR N2, GIVEN HERE FOR H2) (3.536E+18/-0.8/0.0) H +O2 (+M) =HO2 (+M) 2.100E+18 -0.800 0.0 H2 /1.0 /H2O /6.5 /O2 /0.4 /AR /0.35 /N2 /0.67 /CO /0.75 /CO2 /1.5 /CH4 /3.0 / !---- CEC 94 (1.690E+14/0/3.66), (300-1000 K, dlogk = +-0.3) HO2 +H =OH +OH 1.500E+14 0.0 3.800 !---- CEC 94 (4.280E+13/0/5.90), (300-1000 K, dlogk = +-0.3) HO2 +H =H2 +O2 3.000E+13 0.0 4.000 !---- OK CEC 94 (3.011E+13/0/7.20), (300-1000 K, dlog k = +-0.3) HO2 +H =H2O +O 3.000E+13 0.0 7.200 !---- CEC 94 (3.19E+13/0/0), (300-1000 K, dlogk = +-0.3 rising to +-0.5) HO2 +O =OH +O2 2.000E+13 0.0 0.0 !---- CEC 94, k=(2.89E+13/0/-2.08), (300-2000K, dlogk = +-0.2 rising to +-0.5) HO2 +OH =H2O +O2 6.000E+13 0.0 0.0 !****************************************** !**** 04. H2O2 Formation/Consumption !****************************************** !---- CEC 94 (4.22E+14/0/50.14) (850-1250 K) OR !---- CEC 94 (4.22E+14/0/50.14+1.32E+11/0/-6.82) (550-1250 K, +-0.15 to +-0.4) HO2 +HO2 =H2O2 +O2 4.220E+14 0.0 50.140 !**** BEGIN DUPLICATE REACTION DUPLICATE HO2 +HO2 =H2O2 +O2 1.320E+11 0.0 -6.820 !**** END DUPLICATE REACTION DUPLICATE !---- CEC 94, k_inf=(7.23E13/-0.37/0.00), (200-1500K, dlog k=+-0.5) !---- k_0(N2)=(5.53E19/-0.76/0.00), (250-1400K, dlog k=+-0.4) !---- Fcent(N2)=(0.50) , (200-1500K, dFc = +- 0.2) OH +OH (+M) =H2O2 (+M) 7.230E+13 -0.370 0.0 LOW / 5.530E+19 -0.760 0.0 / TROE / 0.500 1.0E-30 1.0E+30 / H2 /1.0 /H2O /6.5 /O2 /0.4 /AR /0.35 /N2 /0.4 /CO /0.75 /CO2 /1.5 /CH4 /3.0 / !---- OK CEC 94 (1.686E+12/0/15.71), (300-1000 K, dlogk = +-0.3) H2O2 +H =H2 +HO2 1.700E+12 0.0 15.700 !---- OK CEC 94 (1.024E+13/0/14.97) (300-1000 K , dlogk = +-0.3) H2O2 +H =H2O +OH 1.000E+13 0.0 15.000 !---- CEC 94 (6.62E+11/0/16.63) (300-500 K, +-0.3) !---- 86 TSA/HAM (9.63E+06/2.0/16.629) (300-2500 K) H2O2 +O =OH +HO2 9.630E+06 2.0 16.630 !---- CEC 94 k=(7.82E+12/0/5.57), (300-1000 K, dlogk = +-0.2 rising to +-0.5) H2O2 +OH =H2O +HO2 5.400E+12 0.0 4.200 !****************************************** !**** 05. CO REACTIONS !****************************************** !---- GRI 2.11, k=(4.76E+07/1.23/0.29) !---- 76 BAU/DRY, k=(1.51E+07/1.3/-3.2), (250-2000K, dlog k = +-0.5) !---- 94 BAU/COB, k=(6.32E+06/1.5/-2.08), (300-2000K, dlog k = +-0.2 at 300K r.to +-0.5) !---- attention 94 BAU/COB evaluation is based on wrong flame velocity measurements !---- 76 BAU/DRY are in better agreement to direct kinetic measurements CO +OH =CO2 +H 4.760E+07 1.230 0.290 !---- 86 TSA/HAM (1.50E+14/0/98.94), (300-2500K) CO +HO2 =CO2 +OH 1.500E+14 0.0 98.700 !---- 86 TSA/HAM, k(N2)=(6.170E+14/0/12.56), here given for H2 CO +O (+M) =CO2 (+M) 1.540E+15 0.0 12.560 H2 /1.0 /H2O /6.5 /O2 /0.4 /AR /0.35 /N2 /0.4 /CO /0.75 /CO2 /1.5 /CH4 /3.0 / !---- 86 TSA/HAM (2.53E+12/0/199.54) (300-2500 K, delta = +-2) CO +O2 =CO2 +O 2.500E+12 0.0 200.000 !****************************************** !---- !---- !---- !****************************************** !**** 10. CH Reactions !****************************************** !---- OK CEC 94, k=(3.98E=13/0/0), (300-2000K ,dlog k = +-0.5) CH +O =CO +H 4.000E+13 0.0 0.0 !---- CEC 94, k=(3.312E+13/0/0), (300-2000K, dlog k= +-0.3 r. to +-0.5 at 2000K) !---- products:(CHO+O),(CO+OH),no branching ratio !****CH +O2 =CHO +O 3.000E+13 0.0 0.0 !****adjusted to total ion concentrations, J.Prager 12/04/2005 !****new recom. say 1.686E+13 with error of factor 2 CH +O2 =CHO +O 0.843E+13 0.0 0.0 !---- CEC 94, k=(3.43E+12/0/2.87), (300-1000K, dlog k = +-0.1) CH +CO2 =CHO +CO 3.400E+12 0.0 2.900 !---- CEC 94, k=5.721E+12/0/-3.16), (300-1000K, dlog k = +-0.1) CH +H2O =CH2O +H 4.560E+12 0.0 -3.200 CH +H2O =Th-CH2 +OH 1.140E+12 0.0 -3.200 !---- Miller,Bowman Prog. Energy Combust.Sci. 15,287, (1989) CH +OH =CHO +H 3.000E+13 0.0 0.0 !****************************************** !**** 11. CHO REACTIONS !****************************************** !---- CEC 94, k=(4.474E14/0/65.93) meas. AR, here given for H2, !---- k_r=(5.492E+14/0/3.076) meas. AR, here given for H2 !---- for k (600-2500K, dlogk = +-0.5); for k_r (300-2500K, dlogk = +-0.5) CHO (+M) =CO +H (+M) 4.500E+14 0.0 66.000 H2 /1.0 /H2O /6.5 /O2 /0.4 /AR /0.35 /N2 /0.4 /CO /0.75 /CO2 /1.5 /CH4 /3.0 / !---- OK CEC 94 (300-2500 K, dlogk = +-0.3) CHO +H =CO +H2 9.000E+13 0.0 0.0 !---- OK CEC 94 (300-2500 K, dlogk = +-0.3) CHO +O =CO +OH 3.000E+13 0.0 0.0 !---- OK CEC 94 (300-2500 K, dlogk = +-0.3) CHO +O =CO2 +H 3.000E+13 0.0 0.0 !---- OK CEC 94 (300-2500 K, dlogk = +-0.3) CHO +OH =CO +H2O 1.000E+14 0.0 0.0 !---- OK CEC 94 k_sum=(3.011E+12/0/0) (300-2500 K, dlogk=+-0.3), !---- (CO+HO2),(OH+CO2),(HCO3); (CO+HO2) main channel, (HCO3) not relevant CHO +O2 =CO +HO2 3.000E+12 0.0 0.0 !---- OK CEC 94 (300 K, dlogk = +-0.3) CHO +CHO =CH2O +CO 3.000E+13 0.0 0.0 !****************************************** !**** 12. CH2 Reactions !****************************************** !---- CEC 94, k=(6.022E+12/0/-7.48), (300-3000K, dlog k = +-0.7) Th-CH2 +H =CH +H2 6.000E+12 0.0 -7.500 !---- CEC 94, k=(1.204E+14/0/0),(300-2500K, dlog k=+-0.2 rising to +-0.7 at 2500K) !---- Products: (CO+H+H), (CO+H2); k1/k=0.6+-0.3 over whole range Th-CH2 +O =>CO +H +H 7.600E+13 0.0 0.0 !---- CEC 94, k=(1.204E+14/0/3.326),(300-3000K, dlog k = +-0.5) !---- products: (C2H2+H+H),(C2H2+H2), k2/k=0.9 =-0.1 over range 300-3000K Th-CH2 +Th-CH2 =C2H2 +H2 1.200E+13 0.0 3.4 Th-CH2 +Th-CH2 =C2H2 +H +H 1.100E+14 0.0 3.4 !---- CEC 94, k=(4.215E+13/0/0), (300-3000K, dlog k=+-0.3 r. to +-0.5 at 3000K) Th-CH2 +CH3 =C2H4 +H 4.200E+13 0.0 0.0 !---- 2 NEXT REACT.: OK CEC 89. THESE ARE THE 2 FASTEST REACTIONS. !---- CEC 94, k=(2.469E+13/0/6.236),(300-1000K,dlog k= +-0.1 r. to +-0.5 at 1000K) !---- O2+CH2=>(CO2+H2)(CO2+H+H)(CO+OH+H)(CO+H2O)(CH2O+O) Th-CH2 +O2 =CO +OH +H 1.300E+13 0.0 6.200 Th-CH2 +O2 =CO2 +H2 1.200E+13 0.0 6.200 !---- CEC 94, scaled AR: k=(1.050E+13/0/0),(300-2000K, dlog k = +-0.3) !---- CEC 94, scaled N2: k=(1.510E+13/0/0),(300-2000K, dlog k = +-0.3) !---- only for H2, O2, H2O, CO, CO2, (N2 or AR) On-CH2 (+M) =Th-CH2 (+M) 1.200E+13 0.0 0.0 H2 /1.0 /H2O /6.5 /O2 /0.4 /AR /0.35 /N2 /0.4 /CO /0.75 /CO2 /1.5 /CH4 /3.0 / !---- CEC 94, k=(3.132E+13/0/0), (300-1000K, dlog k= +-0.3 r. to +-0.5 at 1000K) !---- procuts: ONLY THIS CHANNEL On-CH2 +O2 =CO +OH +H 3.100E+13 0.0 0.0 !---- OK CEC. WITH REVERSE REACTION THOUGH THE REV. ONE IS SO COMPETITIV !---- CEC 94, k_r=(6.02E+13/0/63.19), (300-2500K, dlog k= +-1.0) CH3 +H =On-CH2 +H2 6.000E+13 0.0 63.2 !---- additional reactions !---- see above Th-CH2 +O =CO +H2 4.400E+13 0.0 0.0 !****************************************** !**** 13. CH2O Reactions !****************************************** !---- CEC 94, k=k1+k2=(4.646E+36/-5.54/404.58), (1700-3200, dlog k = +-0.3) !---- products: (CHO+H+M),(CO+H2+M), k2/k= 0.7 +-0.4, 2000-3000K CH2O (+M) =CHO +H (+M) 1.400E+36 -5.54 404.580 H2 /1.0 /H2O /6.5 /O2 /0.4 /AR /0.35 /N2 /0.4 /CO /0.75 /CO2 /1.5 /CH4 /3.0 / !---- CEC 94 (1.265E+08/1.62/9.062) (300-1700 K, dlogk = +-0.1 rising to +-0.3) CH2O +H =CHO +H2 1.270E+08 1.62 9.000 !---- OK CEC 94 (250- 2000K, dlogk = +-0.1 rising to +-0.3) CH2O +O =CHO +OH 4.150E+11 0.57 11.600 !---- OK CEC 94 (3.43E+09/1.18/-1.87) (300-3000 K,dlogk = +-0.1 rising to +-0.7) CH2O +OH =CHO +H2O 3.400E+09 1.18 -1.870 !---- OK CEC 94 (600-1000 K, dlogk = +-0.5) CH2O +HO2 =CHO +H2O2 3.000E+12 0.0 54.7 !---- CEC 94, k=(7.83E-08/6.1/8.23), (300-2000K, dlog k = +-0.2) CH2O +CH3 =CHO +CH4 7.830E-08 6.1 8.200 !---- OK CEC 94 k=(6.020E+13/0/170.10), (700-1000 K, dlog k = +-0.5) CH2O +O2 =CHO +HO2 6.000E+13 0.0 170.700 !---- additional reactions !---- see above CH2O (+M) =H2 +CO (+M) 3.250E+36 -5.54 404.580 H2 /1.0 /H2O /6.5 /O2 /0.4 /AR /0.35 /N2 /0.4 /CO /0.75 /CO2 /1.5 /CH4 /3.0 / !****************************************** !**** 14. CH3 Reactions !****************************************** !---- CEC 94, k=(1.0E+16/0/379.1), (1500-3000K, dlog k = +-0.5) CH3 (+M) =Th-CH2 +H (+M) 1.000E+16 0.0 379.000 H2 /1.0 /H2O /6.5 /O2 /0.4 /AR /0.35 /N2 /0.4 /CO /0.75 /CO2 /1.5 /CH4 /3.0 / !---- M. W. Markus, D. Woiki, P. Roth, Symp. (Int.) on Comb., 24, 581, (1992) CH3 (+M) =CH +H2 (+M) 6.900E+14 0.0 345.03 H2 /1.0 /H2O /6.5 /O2 /0.4 /AR /0.35 /N2 /0.4 /CO /0.75 /CO2 /1.5 /CH4 /3.0 / !---- CEC 94, k=(4.22E13/0.00/0.00), (300-3000K, dlog k + =-0.4), educt CH2 On-CH2 +CH3 =C2H4 +H 1.600E+13 0.00 -2.38 !---- CEC 94, k=(8.43E+13/0/0), (300-2500K, dlog k = +-0.2) CH3 +O =CH2O +H 8.430E+13 0.0 0.0 !---- CEC 94, k_inf=(2.40E16/0.00/439.01), (1000-3000K, dlog k=+-0.5) !---- k_0(AR)=(4.52E17/0.00/379.97), (1000-1700K, dlog k=+-0.3),1.29e+18 !---- Fcent(N2)=(0.0/1350/1.0/7830) , (1000-5000K, dFc = +- 0.1) CH4 (+M) =CH3 +H (+M) 2.400E+16 0.000 439.00 LOW / 1.290E+18 0.000 379.97 / TROE / 0.000 1350.0 1.0 7830.0 / H2 /1.0 /H2O /6.5 /O2 /0.4 /AR /0.35 /N2 /0.4 /CO /0.75 /CO2 /1.5 /CH4 /0.66 / !---- NEXT REACT: T.M. SLOANE CST 63, PP287-313 (1989). FORW. REAC. CH3 +OH =>CH3O +H 4.000E+14 0.0 64.8 CH3O +H =>CH3 +OH 4.750E+16 -0.13 88.0 !---- CEC 94, k=(7.23E+13/0/11.64), (300-1000K dlog k = +-0.5) CH3 +OH =On-CH2 +H2O 3.000E+13 0.0 11.64 !---- CEC 94, k1=(3.312E+11/0/37.41), (1000-2500K, dlog k= +-0.5) !---- products: (CH2O+OH),(CH3O+O),(CH3O2) see in the mechanism !---- this is the favoured route CH3 +O2 =CH2O +OH 1.700E+11 0.0 37.400 !---- CEC 94, k=(1.8E+13/0/0), (300-2500K, dlog k = +-0.7) CH3 +HO2 =CH3O +OH 1.600E+13 0.0 0.0 !---- CEC 94, k=(3.975E13/0/238.03), !---- (500-2500K, dlog k = =-0.5 at 500K rising to -=1.0 at 2000K) CH4 +O2 =CH3 +HO2 3.900E+13 0.0 238.0 !---- CEC 94, k_inf=(3.61E13/0.0/0.00), (300-2000K, dlog k=+-0.3) !---- k_0(AR)=(1.27E41/-7.0/11.56), (300-2000K, dlog k=+-0.3),3.63e41 !---- Fcent(AR)=(0.62/73/1180/0) , (300-2000K, dFc = +- 0.1) CH3 +CH3 (+M) =C2H6 (+M) 3.610E+13 0.000 0.00 LOW / 3.630E+41 -7.000 11.60 / TROE / 0.620 73.0 1180.0 0.0 / H2 /1.0 /H2O /6.5 /O2 /0.4 /AR /0.35 /N2 /0.4 /CO /0.75 /CO2 /1.5 /CH4 /3.0 / !****************************************** !**** 15a. CH3O Reactions !****************************************** !---- OK WA 84 /2 VALUE STEADILY CHANGING. CEC 89 TOO FAST. CEC 91 KNOWN !---- 2 YEARS TOO LATE CH3O (+M) =CH2O +H (+M) 5.000E+13 0.0 105.0 H2 /1.0 /H2O /6.5 /O2 /0.4 /AR /0.35 /N2 /0.4 /CO /0.75 /CO2 /1.5 /CH4 /3.0 / !---- CEC 94, k=(1.8E+13/0/0), (300-1000K, dlog k = +-0.5) CH3O +H =CH2O +H2 1.800E+13 0.0 0.0 !---- CEC 94, k=(2.170E+10/0/7.3), (300-1000K, !---- dlog k= +-0.1 at 500K rising to +-0.3 ar 300K and 1000K) CH3O +O2 =CH2O +HO2 3.000E+10 0.0 8.9 !---- Konnov CH2O +CH3O =CH3OH +CHO 1.150E+11 0.0 5.2 !---- CEC 94, k=(1.506E+13/0/0),(300-1000K, !---- dlog k= +-0.3 rising to +-0.7 at 1000K) !---- products: (O2+CH3),(OH+CH2O); k2/k=(0.12+-0.1) at 300K !---- k_r1=(1.32E+14/0/131.36), (300-2500K, dlog k = +-0.5) CH3O +O =>O2 +CH3 1.320E+13 0.0 0.0 CH3 +O2 =>O +CH3O 0.600E+14 0.0 131.0 CH3O +O =OH +CH2O 1.800E+12 0.0 0.0 !---- additional reactions !---- 86 TSA/HAM, k=(1.81E+13/0/0), (300-2500K, dlog k = +-0.7) CH3O +OH =CH2O +H2O 1.810E+13 0.0 0.0 !****************************************** !**** 15b. CH2OH Reactions !****************************************** !---- OK WA 84 /2 NO REC. CEC. !---- 89HID/OKI2, k(Ar)=(4.40E15/0/125.6), (1372-1842K, dlog k = +-1.0) CH2OH (+M) =CH2O +H (+M) 5.000E+13 0.0 105.0 H2 /1.0 /H2O /6.5 /O2 /0.4 /AR /0.35 /N2 /0.4 /CO /0.75 /CO2 /1.5 /CH4 /3.0 / !---- OK WA 84 NO REC CEC (1.8E13 FOR CH3O) CH2OH +H =CH2O +H2 3.000E+13 0.0 0.0 !---- CEC 94, (300-1200K, dlog k= +-0.1 at 300K rising to +-0.3 at 1200K) !---- k=(1.570E+15 -1.0 0.0+7.230E+13 0.0 14.97) CH2OH +O2 =CH2O +HO2 1.570E+15 -1.0 0.0 !**** BEGIN DUPLICATE REACTION DUPLICATE CH2OH +O2 =CH2O +HO2 7.230E+13 0.0 14.97 !**** END DUPLICATE REACTION DUPLICATE !---- additional reactions CH2OH +H =CH3 +OH 1.000E+13 0.0 0.0 !****************************************** !**** 16. CH3O2 Reactions !****************************************** !---- 22ND SYMP. NO REC CEC !---- fall-off reaction !---- A. Konnov 1998 CH3 +O2 (+M) =CH3O2 (+M) 7.800E+08 1.2 0.0 LOW / 1.650E+26 -3.300 0.0 / TROE / 0.495 2325.5 10.0 0.0 / H2 /1.0 /H2O /6.5 /O2 /0.4 /AR /0.35 /N2 /0.4 /CO /0.75 /CO2 /1.5 /CH4 /3.0 / !---- Konnov 1998 CH3O2 +CH2O =CH3O2H +CHO 0.130E+12 0.0 37.7 !---- Konnov 1998 CH3O2 +CH3 =CH3O +CH3O 1.500E+13 0.0 -5.0 !---- CEC 94, k=(2.470E+11/0/-6.57), !---- (298-700K, dlog k= +-0.1 at 298K rising to +-0.3 at 700K) CH3O2 +HO2 =CH3O2H +O2 2.400E+11 0.0 -6.6 !---- CEC 94, (298-700K, dlog k= +-0.1 at 298K increasing to +-0.3 at 700K) !---- k=(5.480E+10/0/-3.49), products: (CH3O+CH3O+O2), (CH3OH+CH2O+O2) !---- k1/k2=25exp(-1170/T) CH3O2 +CH3O2 =>CH2O +CH3OH +O2 2.800E+10 0.0 -3.3 CH3O2 +CH3O2 =>CH3O +CH3O +O2 2.700E+10 0.0 -3.3 !****************************************** !**** 17. CH4 Reactions !****************************************** !---- CEC 94, k=(1.325E+04 3.000 33.630), (300-2500K, dlog k = +-0.2 !---- at 300 and 2500K reducing to +-0.05 over the range 500-1000K !---- CEC 94, k_r=(6.865E+03/2.74/39.41), dlog k=+-0.3, 300-2500K CH4 +H =H2 +CH3 1.330E+04 3.000 33.630 !---- CEC 94, k=(7.230E+08 1.560 35.500) !---- (300-2500K, dlog k= +-0.3 falling to +-0.15 at 2500K) CH4 +O =OH +CH3 6.900E+08 1.560 35.500 !---- CEC 94, k=(1.57E+07/1.83/11.64),(250-2500K, dlog k=+-0.07 rising to 0.15) CH4 +OH =H2O +CH3 1.540E+07 1.830 11.600 !---- CEC 94, k=(9.0E+12/0.0/103.4),(600-1000K, dlog k=+-0.2 rising to +-0.3 at 1000K) CH4 +HO2 =H2O2 +CH3 1.000E+13 0.0 103.100 !---- CEC 94, k=(3.000E+13 0.0 -1.660), (200-700K, dlog k = +-1.0) CH4 +CH =C2H4 +H 3.000E+13 0.0 -1.700 !---- 85BOH/DOB, k=(4.300E+12/0/42.0), 296-707K, delta=1.0 CH4 +Th-CH2 =CH3 +CH3 4.300E+12 0.0 42.000 !****************************************** !**** 18. CH3OH Reactions !****************************************** !---- CEC 94, k_inf=(6.022E+13/0/0), (300-2000K, dlog k=+-0.3) !---- k_0 =(4.56E+44/-8.2/0), (1000-2000K, dlog k=+-0.5), meas. AR, given H2 !---- Fc=(0.82/200/1438/0), (1000-2000K, dFc=+-0.1) for AR CH3 +OH (+M) =CH3OH (+M) 6.000E+13 0.000 0.00 LOW / 4.560E+44 -8.200 0.00 / TROE / 0.820 200.0 1438.0 0.0 / H2 /1.0 /H2O /6.5 /O2 /0.4 /AR /0.35 /N2 /0.4 /CO /0.75 /CO2 /1.5 /CH4 /3.0 / !---- Konnov 1998 CH3OH +H =CH2OH +H2 3.100E+13 0.0 25.5 CH3OH +H =CH3O +H2 0.900E+13 0.0 25.5 !---- Konnov 1998 CH3OH +O =CH2OH +OH 3.880E+05 2.5 12.89 CH3OH +O =CH3O +OH 1.300E+05 2.5 20.92 !---- Konnov 1998 CH3OH +OH =CH2OH +H2O 3.000E+04 2.65 -3.7 CH3OH +OH =CH3O +H2O 5.300E+03 2.65 -3.7 !---- Konnov 1998 CH3OH +HO2 =CH2OH +H2O2 0.620E+13 0.0 81.1 !---- Konnov 1998 CH3OH +CH3 =CH4 +CH2OH 3.190E+01 3.17 30.0 CH3OH +CH3 =CH4 +CH3O 1.410E+01 3.1 29.0 !---- Konnov 1998 CH3O +CH3OH =CH2OH +CH3OH 1.500E+12 0.0 29.3 !---- Konnov 1998 CH3OH +CH2O =CH3O +CH3O 0.153E+13 0.0 333.2 !---- additional reaction !---- Konnov 1998 CH3OH +O2 =HO2 +CH2OH 2.050E+13 0.0 189.1 !****************************************** !**** 19. CH3O2H Reactions !****************************************** !---- CEC 94, k=(6.0E+14/0/177.10) !---- (500-800K, dlog k = +-0.2 at 600K rising to +-0.5 at 500K and 800K) CH3O2H =CH3O +OH 6.000E+14 0.0 177.1 !---- CEC 94, k=(7.23E+11/0/-1.08) !---- (300-1000K, dlog k = +-0.2 at 300K rising to +-0.4 at 1000K) OH +CH3O2H =H2O +CH3O2 7.300E+11 0.0 -1.0 !---- additional reactions !---- CEC 94, k=(1.987E+13/0/19.87),(300-1000K, dlog k=+-0.3 r. to +-0.5 at 1000K) O +CH3O2H =OH +CH3O2 1.990E+13 0.0 19.90 !---- Konnov 1998 CH3O2 +H2O2 =CH3O2H +HO2 2.400E+12 0.0 41.80 !---- Konnov 1998 CH3O2 +CH4 =CH3O2H +CH3 1.810E+11 0.0 77.80 !---- Konnov 1998 CH3O2 +CH3OH =CH3O2H +CH2OH 1.810E+11 0.0 57.70 !****************************** !**** * !**** 4. C2 MECHANISM C * !**** * !****************************** !****************************************** !**** 20. C2H REACTIONS !****************************************** !---- CEC 94, k= (1.024E+13/0/0), (300-2500K, dlog k = +-1.0) C2H +O =CO +CH 1.000E+13 0.0 0.0 !---- CEC 94, k=(1.81E+13/0/0), (300K, dlog k = +-0.5) !---- products: (HCCO+O),(CH+CO2),(H+CO+CO),(O+C2HO),(CHO+OH) C2H +O2 =HCCO +O 3.000E+12 0.0 0.0 !---- additional reactions C2H +O2 =CO2 +CH 9.000E+12 0.0 0.0 !---- CEC 94, k=(1.81E+12/0/0), (298 K, dlog k = +- 1.0) C2H +CH4 =C2H2 +CH3 1.810E+12 0.0 0.0 !****************************************** !**** 20A. HCCO REACTIONS !****************************************** !---- CEC 94, k=(1.506E+14/0/0), (300-2500K, dlog k = +-0.4) !---- products: (CH2+CO), (H2+C2O), (HCCOH); only first considered here HCCO +H =Th-CH2 +CO 1.400E+14 0.0 0.0 !---- CEC 94, k=(9.635E+13 0.0 0.0), (300-2500K, dlog k= +-0.3) !---- WITHOUT REVERSE REACTION (NO ELEMENTARY REACTION) HCCO +O =>CO +CO +H 9.640E+13 0.0 0.0 !---- JA MILLER, RE MITCHELL, MD SMOOKE, RJ KEE, 19TH SYMP., 181-96,1982 !---- NO REC. CEC HCCO +Th-CH2 =C2H3 +CO 3.000E+13 0.0 0.0 !---- additional reactions !---- CEC 94, k=(2.77E+11/0/-7.15), (300-1000K, dlog k = +-1.0) !---- products: (HCCO),(H+C2O) CH +CO =HCCO 2.800E+11 0.0 -7.1 !****************************************** !**** 21. C2H2 REACTIONS !****************************************** !---- P FRANK, T JUST, COMB AND FLAME 38, 231, 1980 NO REC. CEC !---- 84 WAR, k(AR)=(4.0E+16/0/447.0), (1500-3000K, dlog k = +-0.5) C2H2 (+M) =C2H +H (+M) 3.600E+16 0.0 446.0 H2 /1.0 /H2O /6.5 /O2 /0.4 /AR /0.35 /N2 /0.4 /CO /0.75 /CO2 /1.5 /CH4 /3.0 / !---- JA MILLER, RE MITCHELL, MD SMOOKE, RJ KEE, 19TH SYMP., 181-96,1982 !---- NO REC CEC C2H2 +O2 =HCCO +OH 2.000E+08 1.5 126.0 !---- CEC 94, k=(6.620E+13/0/116.40),(1000-3000K, dlog k=+-1.0) !---- CEC 94, k_r=(1.080E+13/0/9.06),(300-2500K, dlog k=+-0.4) !---- C2H2+H-=>C2H+H2 C2H2 +H =C2H +H2 6.023E+13 0.0 116.40 !---- CEC 94, k=(7.23E+06/2.1/6.57),(295-2500K, dlog k = +-0.2), !---- k2/k=0.7+-0.2 over the whole range !----VK CEC 1994 (branching ratio 0.3 / 0.7) C2H2 +O =Th-CH2 +CO 2.200E+06 2.1 6.57 C2H2 +O =HCCO +H 5.100E+06 2.1 6.57 !---- CEC 94, k=k1+k2=(6.000E+13/0.0/54.0), (1000-2000K, dlog k = +-1.0) !---- products: (h2o+c2h),(h+ch2co),(c2h2oh), last at low temp. and high press. C2H2 +OH =H2O +C2H 6.200E+13 0.0 54.2 !---- CEC 94, k=(9.0E+13/0.0/0.0), (300-2700K, !---- dlog k = +-0.2 at 298K rising to +-0.5 at 2700K) !----C2H2 +C2H =C4H2 +H 9.000E+13 0.0 0.0 !****************************************** !**** 21A. CH2CO REACTIONS !****************************************** !---- OK WA 84 NO REC CEC, k(Ar)=(3.6e+15/0/247.999), 1000-2000K, dlog k=+-0.5 !---- 86 FRA/BHA, k(Ar)=(2.30E+15/0/241.03), (1650-1850K, dlog k = +- 1.0) CH2CO (+M) =Th-CH2 +CO (+M) 1.000E+16 0.0 248.0 H2 /1.0 /H2O /6.5 /O2 /0.4 /AR /0.35 /N2 /0.4 /CO /0.75 /CO2 /1.5 /CH4 /3.0 / !---- OK CEC 91 TWICE FASTER !---- CEC 94, k=(1.81E+13/0/14.13), (200-2000K, dlog k=+-0.5 rising to 1.0 at !---- 2000K), products: (ch3+co),(ch2cho),(h2+hcco); !---- k2/k is considered small, k3 may be important at high temp. CH2CO +H =CH3 +CO 3.000E+13 0.0 14.1 !---- CEC 94, k=(2.29E+12/0/5.65), (230-500K, dlog k = +-0.3) !---- products: k1=(CH2O+CO),k2=(CHO+H+CO),k3=(CHO+CHO) !---- no rec. are made for the branching ratio, assume CH2CO +O =CH2O +CO 0.750E+12 0.0 5.7 CH2CO +O =>CHO +H +CO 0.750E+12 0.0 5.7 CH2CO +O =CHO +CHO 0.750E+12 0.0 5.7 !---- CEC 94, k=(1.024E+13/0/0), (300-2000K, dlog k= =-1.0) !---- products: (CH2OH+CO), (CH2O+CHO) !---- CH2CO+OH=>(CH3+CO2)(CH2OH+CO)(CH3O+CO)(HCO+CH2O)(HCCO+H2O)(CH2O+H+CO) !---- k(overall)= 7.20E12 0.00 0.00 D/U 296 [92OEH/TEM] !---- According to the measurements of [94GRU/NOL] !---- k(2)/k=0.60+-0.10; k(4)/k<0.02; k(5)/k<0.01; estimated: k(1)/k= 0.25 !---- here k(1)/k= 0.35 and k(2)/k= 0.65 CH2CO +OH =CH3 +CO2 2.520E+12 0.0 0.0 CH2CO +OH =CH2O +CHO 4.680E+12 0.0 0.0 !****************************************** !**** 25. C2H3 REACTIONS !****************************************** !---- CEC 94, k_inf=(2.00E14/0.00/166.28), (500-2500K, dlog k=+-0.5) !---- k_0(AR+N2)=(4.16E41/-7.5/190.39), (500-2500K, dlog k=+-0.5) !---- 1.187e+42, 1.039e+42 scaled for H2 !---- Fcent=(0.35) , (500-2500K, dFc = +- 0.1) C2H3 (+M) =C2H2 +H (+M) 1.900E+14 0.000 166.3 LOW / 1.000E+42 -7.500 190.4 / TROE / 0.350 1.0E-30 1.0E+30 / H2 /1.0 /H2O /6.5 /O2 /0.4 /AR /0.35 /N2 /0.4 /CO /0.75 /CO2 /1.5 /CH4 /3.0 / !---- NEXT VALUE FULLY ESTIMATED!!! C2H3 +OH =C2H2 +H2O 5.000E+12 0.0 0.0 !---- CEC 94, k=(1.2E+13/0/0), (300-2500K, dlog k = +-0.5) C2H3 +H =C2H2 +H2 1.200E+13 0.0 0.0 !---- CEC 94, k=(3.01E+13/0/0), (300-2000K, dlog k= +-0.5), 1/3 FOR EACH REACTION C2H3 +O =C2H2 +OH 1.000E+13 0.0 0.0 C2H3 +O =CH3 +CO 1.000E+13 0.0 0.0 C2H3 +O =CHO +Th-CH2 1.000E+13 0.0 0.0 !---- change of resction products, !!!! important note !!!! !---- !!!! then reaction On-CH2 + CH3 ---=> C2H4 + H necessary !!!!! !---- !!!! additional reaction channel CH + H2O ---=> CH2O + H (*) necessary !---- to channel CH + H2O ---=> Th-CH2 + OH (*) too, !---- sum of rate constant for above reaction (*) are equal to !---- recommendation of CEC1992 !!!!! !---- decreases flame velocities to correct magnitude !---- CEC 1992=1994 !---- C2H3+O2=>(CH2O+CHO);(CH2CHO+O);(C2H2+HO2) !---- k1=k-(k(CH2CHO+O)+k(C2H2+HO2)) C2H3 +O2 =CH2O +CHO 5.420E+12 0.0 0.0 DUPLICATE !**** BEGIN DUPLICATE REACTION C2H3 +O2 =CH2O +CHO 7.000E+14 -0.6 13.1 DUPLICATE !**** END DUPLICATE REACTION !----VK Bozzelli, J.w., Dean, A.M., J. Phys. Chem. 92, 651, (1992) !----VK Bozzelli T(high) value C2H3 +O2 =CH2CHO +O 2.460E+15 -0.78 13.12 !---- Mebel 1996 (Lin) (1.340E+06 1.61 -1.61) C2H3 +O2 =C2H2 +HO2 1.340E+06 1.61 -1.61 !****************************************** !**** 22A. CH3CO REACTIONS !****************************************** !---- CEC 94, k_inf=(5.06E11/0/28.77), (300-500K, dlog k=+-0.5) !---- k_0(N2)=(1.52E12/0/ 0.00), (350-350K, dlog k=+-0.5),3.81e12 !---- k_0(HE)=(1.09E14/0/15.88), (400-500K, dlog k=+-0.2),3.11e14 !---- Fcent(N2)=(0.60) , (300-350K, dFc = +- 0.1) !---- Fcent(HE)=(0.50) , (400-500K, dFc = +- 0.1) CH3 +CO (+M) =CH3CO (+M) 5.058E+11 0.000 28.77 LOW / 3.109E+14 0.000 15.88 / TROE / 0.500 1.0E-30 1.0E+30 / H2 /1.0 /H2O /6.5 /O2 /0.4 /AR /0.35 /N2 /0.4 /CO /0.75 /CO2 /1.5 /CH4 /3.0 / !---- OK WA 84 NO REC CEC CH3CO +H =CH2CO +H2 2.000E+13 0.0 0.0 !****************************************** !**** 22B. CH2CHO REACTIONS !****************************************** !---- ANALOGY WITH CH3CO CH2CHO +H =CH2CO +H2 2.000E+13 0.0 0.0 !****************************************** !**** 23. C2H4 REACTIONS !****************************************** !---- CEC 94, k(AR)=(3.490E+16/0.0/299.32), (1500-3200K, dlog k = +-0.3) C2H4 (+M) =C2H2 +H2 (+M) 1.000E+17 0.0 300.0 H2 /1.0 /H2O /6.5 /O2 /0.4 /AR /0.35 /N2 /0.4 /CO /0.75 /CO2 /1.5 /CH4 /3.0 / !---- CEC 94, k(AR)=(2.590E+17/0.0/404.09),(1500-3200K, dlog k = +-0.5) C2H4 (+M) =C2H3 +H (+M) 7.400E+17 0.0 404.0 H2 /1.0 /H2O /6.5 /O2 /0.4 /AR /0.35 /N2 /0.4 /CO /0.75 /CO2 /1.5 /CH4 /3.0 / !---- CEC 94, k=(5.420E+14 0.0 62.4),(700-2000K, dlog k = +-0.5) C2H4 +H =C2H3 +H2 5.200E+14 0.0 62.4 !---- CEC 94 C2H4+O=>(CH2CHO+H);(CHO+CH3);(CH2O+CH2);(CH2CO+H2) !---- k=(1.355E+07/1.88/0.765) all channel,(300-2000K, dlog k=+-0.1 r. to +-0.3) !---- k1/k=0.35+-0.05, k2/k=0.6+-0.1, k3/k=0, k4/k=0.05+-0.10 at p=>3torr,T=>300K C2H4 +O =CH2CHO +H 4.800E+06 1.88 0.75 C2H4 +O =CHO +CH3 8.100E+06 1.88 0.75 C2H4 +O =CH2CO +H2 6.800E+05 1.88 0.75 !---- CEC 94, k=(2.050E+13 0.0 24.9), (650-1500K, dlog k = +-0.5) C2H4 +OH =C2H3 +H2O 2.050E+13 0.0 24.9 !---- additional reactions !---- CEC 94, k=(9.65E+13/0/0), k2/k=0.2 over range 300-1000K !---- dlog k= +-0.5 at 1000K reducing to +-0.2 at 300K, d(k2/k1)=+-0.1 !----C2H4 +On-CH2 =C3H6 7.240E+13 0.0 0.00 !---- CEC 94, k=(1.32E+14/0/-1.44), (200-700K, dlog k = +- 1.0) !---- products: (C3H4+H),(Th-CH2+C2H3) !----C2H4 +CH =C3H4 +H 1.320E+14 0.0 -1.44 !---- CEC 94, k=(4.16E+12/0/46.56), (400-3000K, dlog k = +-0.5) C2H4 +CH3 =C2H3 +CH4 3.500E+12 0.0 46.60 !****************************************** !**** 23A. CH3CHO REACTIONS !****************************************** !---- fall-off reaction !---- CEC 94, here values given only for p = 1 atm, k=(7.0E+15/0/341.7), !---- (750-1200K, dlog k= +-0.4) CH3CHO (+M) =CH3 +CHO (+M) 2.200E+15 0.0 342.8 LOW / 5.100E+12 0.000 131.4 / TROE / 0.500 1.0E-30 1.0E+30 / H2 /1.0 /H2O /6.5 /O2 /0.4 /AR /0.35 /N2 /0.4 /CO /0.75 /CO2 /1.5 /CH4 /3.0 / !---- CEC 94, k=k1+k2=(4.095E+09/1.16/10.06),(300-2000K, dlog k=+-0.1 r. to +-0.4) CH3CHO +H =CH3CO +H2 2.150E+09 1.16 10.0 CH3CHO +H =CH2CHO +H2 1.850E+09 1.16 10.0 !---- CEC 94, k=k1+k2=(5.84E+12/0/7.57),(298-1500K, dlog k= +-0.05 r. to +-0.5) CH3CHO +O =CH3CO +OH 5.600E+12 0.0 7.6 CH3CHO +O =CH2CHO +OH 2.400E+11 0.0 7.6 !---- CEC 94, k=(3.000E+13/0/163.8),(600-1100K, dlog k = +-0.5 rising to +-1.0) CH3CHO +O2 =CH3CO +HO2 4.000E+13 0.0 164.3 !---- CEC 94, k=(2.35E+10/0.73/-4.66), (250-1200K, dlog k=+-0.1 rising to +-0.3) !---- main channel -=> CH3CO +H2O, other CH2CHO + H2O CH3CHO +OH =CH3CO +H2O 2.300E+10 0.73 -4.6 !---- CEC 94, k=(3.0E+12/0.0/49.9), (900-1200K, dlog k= +-0.7) CH3CHO +HO2 =CH3CO +H2O2 3.100E+12 0.0 50.0 !---- ASK CHRISTA. S. MURIES SAYS WA 84... CH3CHO +Th-CH2 =CH3CO +CH3 2.500E+12 0.0 15.9 !---- CEC 94, k=(2.0E-06/5.60/10.3),(300-1250K, dlog k = +-0.3) CH3CHO +CH3 =CH3CO +CH4 2.050E-06 5.60 10.3 !---- additional reactions !---- see above CH3CHO +OH =CH2CHO +H2O 0.050E+10 0.73 -4.6 !****************************************** !**** 24. C2H5 REACTIONS !****************************************** !---- CEC 94, k_inf=(3.97E09/1.28/5.40), (200-1100K, dlog k=+-0.3) !---- k_0(HE)=(4.71E18/0.00/3.16), (300- 800K, dlog k=+-0.3),1.35e19 !---- k_0(N2)=(2.79E18/0.00/3.16), (300- 800K, dlog k=+-0.3),6.98e18 !---- Fcent(HE,N2)=(0.76/40/1025/0) , (300- 800K, dFc = +- 0.1) C2H4 +H (+M) =>C2H5 (+M) 3.970E+09 1.280 5.40 LOW / 6.980E+18 0.000 3.20 / TROE / 0.760 40.0 1025.0 0.0 / H2 /1.0 /H2O /6.5 /O2 /0.4 /AR /0.35 /N2 /0.4 /CO /0.75 /CO2 /1.5 /CH4 /3.0 / !---- CEC 94, k_inf=(8.20E13/0/166.86), (700-1100K, dlog k=+-0.3) !---- k_0(C2H6)=(1.02E18/0/139.68), (700- 900K, dlog k=+-0.3),3.41e17 !---- Fcent(C2H6)=(0.75/97/1379/0) , (700-1100K, dFc = +- 0.1) C2H5 (+M) =>C2H4 +H (+M) 8.200E+13 0.000 166.80 LOW / 3.400E+17 0.000 139.60 / TROE / 0.750 97.0 1379.0 0.0 / H2 /1.0 /H2O /6.5 /O2 /0.4 /AR /0.35 /N2 /0.4 /CO /0.75 /CO2 /1.5 /CH4 /3.0 / !---- CEC 94, k = (3.61E+13/0/0), (300K-2000K, dlog k=+-0.3 at 300K rising to !---- +-0.7 at 2000K) !---- k_r=(3.01E+13/0/56.54), (1300-2500K, dlog k= +-0.6) C2H5 +H =CH3 +CH3 6.000E+13 0.0 0.0 !---- CEC 94, (300-2500K, dlog k=+-0.3 from 300K to 1000K,+-0.5 from 1000K-2500K) !---- k=(6.62E+13/0/0), k2/k= 0.17+-0.2 at 300K C2H5 +O =CH3CHO +H 5.320E+13 0.0 0.0 C2H5 +O =CH2O +CH3 1.300E+13 0.0 0.0 !---- CEC 94, k=(1.020E+10/0.0/-9.15), (600-1200K, dlog k = +-0.3) C2H5 +O2 =C2H4 +HO2 1.000E+10 0.0 -9.1 !---- CEC 94, k=(1.14e+12/0/0), (300-800K, dlog k =+-0.4) C2H5 +CH3 =C2H4 +CH4 1.140E+12 0.0 0.0 !---- CEC 94, k=(1.450E+12/0.0/0.0),(300-1200, dlog k = +-0.4) C2H5 +C2H5 =C2H4 +C2H6 1.400E+12 0.0 0.0 !****************************************** !**** 30B. C2H5O REACTIONS !****************************************** !---- HEI 298-450 C2H5O =CH3CHO +H 2.000E+14 0.0 97.0 !---- CEC 94, k=(8.000E+13/0/90.0), (300-600K, dlog k = +-1.0, est.) C2H5O =CH2O +CH3 8.000E+13 0.0 90.0 !---- CEC 94, k=(6.020E+10/0/6.9), (300-1000K, dlog k = +-0.3 rising to +-0.5 at 1000K) C2H5O +O2 =CH3CHO +HO2 6.000E+10 0.0 7.0 !---- Konnov 1998 C2H5O +OH =CH3CHO +H2O 1.000E+14 0.0 0.0 !---- Konnov 1998 C2H5O +H =CH3CHO +H2 1.000E+14 0.0 0.0 !---- Konnov 1998 C2H5O +O =CH3CHO +OH 1.210E+14 0.0 0.0 !****************************************** !**** 30C. CH3CHOH REACTIONS !****************************************** !---- SAME AS FOR CH2OH, OK WA 84 NO REC CEC CH3CHOH =CH3CHO +H 1.000E+14 0.0 105.0 !---- SAME AS FOR CH2OH, OK WA 84 NO REC CEC CH3CHOH +H =CH3CHO +H2 3.000E+13 0.0 0.0 !---- HH GROTHEER, FL NESBITT, RB KLEMM, J. PHYS. CHEM. 54, 984, 1976 !---- NO REC CEC CH3CHOH +OH =CH3CHO +H2O 1.510E+13 0.0 0.0 !---- HH GROTHEER, FL NESBITT, RB KLEMM, J. PHYS. CHEM. 54, 984, 1976 !---- NO REC CEC CH3CHOH +O =CH3CHO +OH 1.200E+14 0.0 0.0 !---- HH GROTHEER, FL NESBITT, RB KLEMM, J. PHYS. CHEM. 54, 984, 1976 !---- NO REC CEC CH3CHOH +O2 =CH3CHO +HO2 1.200E+13 0.0 0.0 !****************************************** !**** 30D. CH2CH2OH REACTIONS !****************************************** !---- BETA-DECOMP. ESTIMATED. NO REC CEC CH2CH2OH =C2H4 +OH 1.000E+14 0.0 140.0 !---- M BARTELS, K HOYERMANN, R SIEVERT, 19TH SYMP. COMB., 61, 1982 !---- NO REC CEC CH2CH2OH+H =CH3CHO +H2 5.000E+13 0.0 0.0 !****************************************** !**** 31. C2H5OH REACTIONS !****************************************** !---- Konnov 1998 C2H5OH =CH3 +CH2OH 3.100E+15 0.0 337.2 !---- Konnov 1998 C2H5OH =C2H5 +OH 5.000E+16 0.0 381.6 !---- Konnov 1998 C2H5OH =C2H4 +H2O 1.000E+14 0.0 320.9 !---- R ATKINSON, INT. J. CHEM. KINET. 18, 555-68, 1986 NO REC CEC C2H5OH +OH =CH3CHOH +H2O 5.250E+06 2.0 1.9 C2H5OH +OH =C2H5O +H2O 1.150E+06 2.0 3.8 C2H5OH +OH =CH2CH2OH+H2O 8.130E+06 2.0 2.5 !---- ESTIMATED NO REC CEC C2H5OH +O =CH3CHOH +OH 7.940E+12 0.0 13.6 !---- HH GROTHEER, FL NESBITT, RB KLEMM, J.PHYS. CHEM. 90, 2512, 1986 !---- NO REC CEC C2H5OH +O =C2H5O +OH 4.790E+13 0.0 28.7 !---- ESTIMATED NO REC CEC C2H5OH +O =CH2CH2OH+OH 1.000E+14 0.0 31.3 !---- WK ADERS, HGG WAGNER, BER. BUNSENGES, PHYS. CHEM. 77, 712, 1973 !---- NO REC CEC C2H5OH +H =CH3CHOH +H2 4.400E+12 0.0 19.1 C2H5OH +H =C2H5 +H2O 5.900E+11 0.0 14.4 !---- SAME AS FOR METHANOL NO REC CEC C2H5OH +HO2 =CH3CHOH +H2O2 6.300E+12 0.0 81.1 !---- REACTION WITH CHO !----C2H5OH +CHO =C2H5O +CH2O 6.500E+09 0.0 57.2 !---- P GRAY, AA HEROD, TRANS. FARADAY SOC. 64, 1568, 1968 NO REC CEC C2H5OH +CH3 =CH3CHOH +CH4 2.040E+11 0.0 36.4 !---- ESTIMATED NO REC CEC C2H5OH +CH3 =CH2CH2OH+CH4 2.040E+11 0.0 36.4 !---- P GRAY, AA HEROD, TRANS. FARADAY SOC. 64, 1568, 1968 NO REC CEC C2H5OH +CH3 =C2H5O +CH4 7.490E+10 0.0 39.3 !---- SAME AS FOR METHANOL NO REC CEC C2H5OH +CH3O =CH3CHOH +CH3OH 2.000E+11 0.0 29.3 !---- SAME AS FOR METHANOL NO REC CEC C2H5OH +CH2O =C2H5O +CH3O 1.530E+12 0.0 333.2 !---- SAME AS FOR CH3O NO REC CEC C2H5OH +C2H5O =C2H5OH +CH3CHOH 2.000E+11 0.0 29.3 !****************************************** !**** 25. C2H6 REACTIONS !****************************************** !---- CEC 94, k=(1.44E+09/1.5/31.0),(300-2000K,dlog k= +-0.15 rising to +-0.3 at 2000K) !---- CEC 94, k_r=(3.07/3.6/35.33), (700-1200K, !---- dlog k = +-0.2 at 700K rising to 0.6 at 1200K) C2H6 +H =C2H5 +H2 1.550E+09 1.5 31.1 !---- CEC 94, k=(1.0E+09/1.5/24.3),(300-1200K,dlog k= +-0.3 falling to +-0.15 at 1200K) C2H6 +O =C2H5 +OH 1.000E+09 1.5 24.4 !---- CEC 94, k=(7.23E+06/2.0/3.62),(250-2000K, dlog k = +-0.07 rising to +-0.15 at 2000K) C2H6 +OH =C2H5 +H2O 7.200E+06 2.0 3.6 !---- CEC 94, k=(1.325E+13/0/85.6),(500-1000K, dlog k= +-0.2 rising to +-0.3 at 1000K) C2H6 +HO2 =C2H5 +H2O2 1.330E+13 0.0 85.9 !---- CEC 94, k=(6.0E+13/0/217.0),(500-2000K, dlog k = +-0.05 rising to +-0.1 at 2000K) C2H6 +O2 =C2H5 +HO2 6.000E+13 0.0 217.0 !---- 22ND SYMP C2H6 +Th-CH2 =C2H5 +CH3 2.200E+13 0.0 36.3 !---- CEC 94, k=(1.51E-07/6/25.3),(300-1500K, dlog k = +-0.1 rising to +-0.2 at 1500K) C2H6 +CH3 =C2H5 +CH4 1.500E-07 6.0 25.4 !---- additional reactions !---- CEC 94, k=(1.08E+14/0/-1.10), (200-700K, dlog k = +-1.0) !---- products: (C2H4+CH3),(C3H6+H) C2H6 +CH =C2H4 +CH3 1.080E+14 0.0 -1.1 !****************************************** !****VK C formation reactions *********** !****************************************** !---- R.L. THORNE, M. C. BRANCH, D. W. CHANDLER, R. J. KEE, J. A. MILLER, !---- SYMP. (INT) COMB., 21, 963, I(86), k=(1.5E+14/0/0) !---- 89BEC/ENG, k=(8.43E+12/0/0), (297, dlog k = +- 1.0) CH +H =C +H2 1.200E+14 0.00 0.0 !---- philip: k=(5.0E+13/0/0) C +O2 =CO +O 5.000E+13 0.00 0.0 !****************************************** !******************************************************************************** !**** MECHANISM OF IONS in CH4/AIR FLAMES Jens Prager 14.10.2003 * !******************************************************************************** !**** * !**** UNITS: Arrhenius parameters: A [cm**3/(mol s)], b [], E [kJ/mol] * !******************************************************************************** !******************************************************************************** !**** CHEMIIONIZATION LEADING TO CHO+ * !******************************************************************************** !---- 6. A.N. Eraslan, R.C. Brown CH +O =CHO+ +E- 2.512E+11 0.0 7.118 !---- 1. H.F. Calcote, R.J. Gill, 1994 CHO+ +E- =CO +H 7.400E+18 -0.68 0.000 !******************************************************************************** !**** REACTIONS INVOLVING H3O+ * !******************************************************************************** !---- 2. UNIST Database CHO+ +H2O =H3O+ +CO 1.506E+15 0.00 0.000 !---- 1. Vincent G. Anicich, JPL Publication 03-19 (2003) CHO+ +C2H5OH =H3O+ +CO +C2H4 6.000E+14 0.00 0.000 !---- 1. A.N. Eraslan, R.C. Brown, Combustion and Flame 94 H3O+ +E- =H2O +H 2.291E+18 -0.50 0.000 !---- 3. Guo Jingzhong, Goodings J.M. (2000) H3O+ +E- =OH +H +H 7.949E+21 -1.37 0.000 !---- 1. S.M. Starikovskaia, A.Yu Starikovskii, D.V. Zatsepin H3O+ +E- =H2 +OH 1.253E+19 -0.50 0.000 !---- 1. UMIST database H3O+ +E- =O +H2 +H 6.000E+17 -0.30 0.000 !---- 1. UMIST database H3O+ +C =CHO+ +H2 6.022E+12 0.00 0.000 !******************************************************************************** !**** REACTIONS INVOLVING C2H3O+ * !******************************************************************************** !---- 1. R.C. Brown, A.N. Eraslan, Combustion and Flame 1988 CHO+ +CH2CO =C2H3O+ +CO 1.259E+15 -0.048 0.000 !---- 1. R.C. Brown, A.N. Eraslan, Combustion and Flame 1988 CHO+ +CH3 =C2H3O+ +H 7.763E+14 -0.006 0.000 !---- 1. R.C. Brown, A.N. Eraslan, Combustion and Flame 1988 C2H3O+ +E- =CH2CO +H 2.291E+18 -0.500 0.000 !---- 1. UMIST database H3O+ +CH2CO =C2H3O+ +H2O 1.204E+15 0.000 0.000 !---- 1. UMIST database C2H3O+ +E- =CO +CH3 2.403E+17 -0.050 0.000 !---- 1. ADO theory !**** C2H3O+ +O =CHO+ +CH2O 3.700E+14 0.000 0.000 !**** adjusted: C2H3O+ +O =CHO+ +CH2O 2.000E+14 0.000 0.000 !******************************************************************************** !**** REACTIONS INVOLVING CH5O+ * !******************************************************************************** !---- 1. R.C. Brown, A.N. Eraslan, Combustion and Flame 1988 CHO+ +CH3OH =CH5O+ +CO 8.710E+14 -0.056 0.000 !---- 3. V.G. Anicich, J. Phys. Chem. Ref. Data 22(6) 1993, 1469-1569 H3O+ +CH3OH =CH5O+ +H2O 1.506E+15 0.000 0.000 !---- 1. UMIST database CH5O+ +E- =CH3OH +H 2.403E+17 -0.050 0.000 !******************************************************************************** !**** EQUILIBIUM C2H3O+ AND CH5O+ * !******************************************************************************** !---- direct proton transfer, 1. ADO theory CH5O+ +CH2CO =C2H3O+ +CH3OH 1.486E+15 -0.077 -0.347 !******************************************************************************** !**** REACTIONS INVOLVING O2- * !******************************************************************************** !---- 3. M. Capitelli, C.M. Ferreira, B.F. Gordiets, A.I. Osipov O2 +E- +O =O2- +O 3.627E+16 0.00 0.000 !---- 4. M. Capitelli, C.M. Ferreira, B.F. Gordiets, A.I. Osipov O2 +E- +O2 =O2- +O2 1.523E+21 -1.00 4.989 !---- 1. M. Capitelli, C.M. Ferreira, B.F. Gordiets, A.I. Osipov O2 +E- +H2O =O2- +H2O 5.077E+18 0.00 0.000 !---- 4. M. Capitelli, C.M. Ferreira, B.F. Gordiets, A.I. Osipov !**** only if N2 is in the mechanism: !****O2 +E- +N2 =O2- +N2 3.590E+21 -2.00 0.582 !---- 1. Filimonova (ions_Filimonova.rct) O2- +H2 =H2O2 +E- 6.022E+14 0.00 0.000 !---- 2. S.M. Starikovskaia, A.Yu Starikovskii, D.V. Zatsepin O2- +H =HO2 +E- 7.226E+14 0.00 0.000 !---- 1. A.M. Starik, N.S. Titova O2- +C2H3O+ =O2 +CH3CO 2.090E+18 -0.50 0.000 !******************************************************************************** !**** REACTIONS INVOLVING OH- * !******************************************************************************** !---- 2. A.N. Hayhurst O2- +OH =OH- +O2 6.022E+13 0.00 0.000 !---- 1. S.M. Starikovskaia, A.Yu Starikovskii, D.V. Zatsepin O2- +H =OH- +O 1.084E+15 0.00 0.000 !---- 3. M. Capitelli, C.M. Ferreira, B.F. Gordiets, A.I. Osipov OH- +O =HO2 +E- 1.204E+14 0.00 0.000 !---- 4. M. Capitelli, C.M. Ferreira, B.F. Gordiets, A.I. Osipov OH- +H =H2O +E- 1.084E+15 0.00 0.000 !---- 1. J.M. Goodings, A.N. Hayhurst E- +OH (+M) =OH- (+M) 1.088E+17 0.00 0.000 H2 /1.0 /H2O /6.5 /O2 /0.4 /AR /0.35 /N2 /0.4 /CO /0.75 /CO2 /1.5 /CH4 /3.0 / !---- 1. UMIST Database Astrochemistry 1999 OH- +C =CHO +E- 3.001E+14 0.00 0.000 !---- 1. UMIST Database Astrochemistry 1999 OH- +CH =CH2O +E- 3.001E+14 0.00 0.000 !---- 1. UMIST Database Astrochemistry 1999 OH- +CH3 =CH3OH +E- 6.022E+14 0.00 0.000 !---- 1. J.M. Goodings, D.K. Bohme, Chun-Wai Ng OH- +CO2 +O2 =CHO3- +O2 2.760E+20 0.00 0.000 !**** just guessed OH- +CO2 +H2O =CHO3- +H2O 1.104E+21 0.00 0.000 !******************************************************************************** !**** REACTIONS INVOLVING CO3- * !******************************************************************************** !---- 1. J.M. Goodings, D.K. Bohme, Chun-Wai Ng CO3- +H =OH- +CO2 1.020E+14 0.00 0.000 !---- 1. A.M. Starik, N.S. Titova CO3- +O =O2- +CO2 4.800E+13 0.00 0.000 !******************************************************************************** !**** SUGGESTED REACTIONS BUT WITHOUT RATE DATA * !******************************************************************************** CHO2- +H =CO2 +H2 +E- 1.159E+14 0.00 0.000 OH- +CHO =CHO2- +H 2.959E+15 -0.14 -0.441 !******************************************************************************** !**** REACTIONS INVOLVING O- * !******************************************************************************** !---- 1. M. Capitelli, C.M. Ferreira, B.F. Gordiets, A.I. Osipov E- +O +O2 =O- +O2 3.627E+16 0.00 0.000 !---- S.M. Starikovskaia, A.Yu Starikovskii, D.V. Zatsepin E- +O +O =O- +O 3.021E+17 0.00 0.000 !---- 1. UMIST - www.rate99.co.uk O- +C =CO +E- 3.011E+14 0.00 0.000 !---- 2. M. Capitelli, C.M. Ferreira, B.F. Gordiets, A.I. Osipov O- +H2 =OH- +H 1.987E+13 0.00 0.000 !---- 3. J.M. Goodings, D.K. Bohme, Chun-Wai Ng O- +CH4 =OH- +CH3 6.022E+13 0.00 0.000 !---- 1. M. Capitelli, C.M. Ferreira, B.F. Gordiets, A.I. Osipov O- +H2O =OH- +OH 8.431E+14 0.00 0.000 !---- 1. D.K.Bohme, J.M. Goodings, Chun-Wai Ng O- +CH2O =OH- +CHO 5.601E+14 0.00 0.000 O- +CH2O =CHO2- +H 1.307E+15 0.00 0.000 !---- 1. A.M. Starik, A.M. Savelev, N.S. Titova, U. Schuhmann O- +C2H6 =C2H5 +OH- 6.130E+15 -0.50 0.000 !---- 1. UMIST - www.rate99.co.uk O- +H =OH +E- 3.011E+14 0.00 0.000 !---- 2. M. Capitelli, C.M. Ferreira, B.F. Gordiets, A.I. Osipov O- +H2 =H2O +E- 4.215E+14 0.00 0.000 !---- 1. UMIST - www.rate99.co.uk O- +CH =CHO +E- 3.011E+14 0.00 0.000 !---- 1. UMIST - www.rate99.co.uk O- +On-CH2 =CH2O +E- 3.011E+14 0.00 0.000 !---- 1. UMIST - www.rate99.co.uk O- +CO =CO2 +E- 3.914E+14 0.00 0.000 !---- 2. M. Capitelli, C.M. Ferreira, B.F. Gordiets, A.I. Osipov O- +O =O2 +E- 8.431E+13 0.00 0.000 !---- 1. J.M. Goodings, D.K. Bohme, Chun-Wai Ng O- +C2H2 =CH2CO +E- 7.226E+14 0.00 0.000 !---- 1. S.M. Starikovskaia, A.Yu Starikovskii, D.V. Zatsepin O- +H2O =H2O2 +E- 3.613E+11 0.00 0.000 !---- 1. M. Capitelli, C.M. Ferreira, B.F. Gordiets, A.I. Osipov O2- +O =O- +O2 1.987E+14 0.00 0.000 !---- 2. J.M. Goodings, D.K. Bohme, Chun-Wai Ng O- +CO2 +O2 =CO3- +O2 1.123E+20 0.00 0.000 !---- 1. A.M. Starik, A.M. Savelev, N.S. Titova, U. Schuhmann O- +C2H3O+ =O +CH3CO 2.090E+18 -0.50 0.000 !******************************************************************************** !**** NEGATIVE-POSITIVE ION REACTIONS * !******************************************************************************** CHO3- +C2H3O+ =CH3CO +CO2 +OH 2.000E+18 0.00 0.000 CHO3- +CH5O+ =CH3OH +H2O +CO2 2.000E+18 0.00 0.000 O- +C2H3O+ =O +CH2CHO 1.000E+18 0.00 0.000 O2- +C2H3O+ =O2 +CH2CO +H 1.000E+18 0.00 0.000 O- +C2H3O+ =O +CH2CO +H 1.000E+18 0.00 0.000 O2- +CH5O+ =O2 +CH3 +H2O 1.000E+18 0.00 0.000 O- +CH5O+ =O +CH3 +H2O 1.000E+18 0.00 0.000 END