! Pierre A. Glaude, P. A., Pitz, W. J., Thomson, M. J., ! "Chemical Kinetic Modeling of Dimethyl Carbonate in an Opposed-Flow Diffusion Flame", ! Proceedings of the Combustion Institute, Volume 30, pp. 1095-1102, 2004. ! Lawrence Livermore National Laboratory, Livermore, CA, UCRL- CONF-201358. ! UCRL-WEB-204236 ! Review and release date: May 19, 2004. ! 4/14/04, mechanism dmc_1i: WJP: Multiply dmc molecular elimination by 2 for degeneracy ! 4/14/04, mechanism dmc_1h: WJP:! TST of dmc molecular elimination ties up 3 rotors not 2 so corrected rate const. ! 4/7/04, mechanism dmc_1g: WJP: Eliminate coc*ooc + h => ch3ocho + ch3o This step is endothermic by 2 kcal ! and would have significant back reaction ! due to exit barrier being 10.8 kcal about the entrance channel. ! 5/9/03, version dmc_1e: coc*ooc radical addition: specify only in forward direction. Reverse rate from thermo not valid. !Specified coc.*o decomposition rates in their reverse direction. ! 5/8/03, version dmc_1d: Added DMC+H addition reactions. Used coc.*o decomposition rates with cbsQ + isodesmic rxn barrier heights by Glaude. ! Added coc*ooh consumption reactions. Added cjoc*ooh and its decomposition ! 5/1/03 Added DMC molecular elimnation reaction. Added methyl carbonate (coc*ooh) and reactions to consume it. !10/30/02: changed methylmethanoate species (mmxxx) that start with an "m" to start with an "am" so that ! chemkin II will work. (chemkin II does not like species to start with "m") !Put DMC species and reactions on top of DMM mechanism version 24 of Henry Curran sent on Oct 14, 2002. !this mechanism can treat dimehtylcarbonate, dimethoxymethane, methylformate, methanol, ethanol and DME oxidation. elements h c o n ar end species h h2 o o2 oh h2o n2 co hco co2 ch3 ch4 ho2 h2o2 ch2o ch3o c2h6 c2h4 c2h5 ch2 ch c2h c2h2 c2h3 ch3oh ch2oh ch2co hcco c2h5oh pc2h4oh sc2h4oh ch3co ch2cho ch3cho ch3coch3 ch3coch2 c2h5cho c2h5co c2h5o ch3o2 c2h5o2 ch3o2h c2h5o2h c2h3o1-2 ch3co2 c2h4o1-2 c2h4o2h o2c2h4oh ch3co3 ch3co3h c2h3co c2h3cho ch3coch2o2 ch3coch2o2h ch3coch2o hco3h hco3 ocho o2c2h4o2h ch2(s) ch3och3 ch3och2 ch3och2o2 ch2och2o2h ch3och2o2h ch3och2o o2ch2och2o2h ho2ch2ocho och2ocho hoch2oco hoch2o hocho ch3och2och3 ch3ochoch3 ch3och2och2 ch3ocho ch3oco ch2ocho ch3och2oh hoch2o2h och2o2h hoch2o2 amm1oo amm1o ammmo ammmoo ammmooh amm1ooh amm1oohmj am1oohm*o ammmooh1j ammcy1om am1oohmoo ammooh1oo chooco ar ! Dimethyl carbonate species coc*ooc coc*oocj coc*ooj coc*ooh cjoc*ooh hoco end reactions cal/mole ch3+h(+m) = ch4(+m) 2.140e+15 -0.40 0.000E+00 low/3.31e+30 -4.0 2108./ troe/0.0 1.e-15 1.e-15 40./ h2/2/ h2o/5/ co/2/ co2/3/ ch4+h = ch3+h2 1.727E+04 3.00 8.224E+03 rev / 6.610E+02 3.00 7.744E+03 / ch4+oh = ch3+h2o 1.930E+05 2.40 2.106E+03 rev / 4.820E+02 2.90 1.486E+04 / ch4+o = ch3+oh 2.130E+06 2.21 6.480E+03 rev / 3.557E+04 2.21 3.920E+03 / c2h6+ch3 = c2h5+ch4 1.510E-07 6.00 6.047E+03 rev / 9.649E-10 6.56 1.022E+04 / hco+oh = co+h2o 1.020E+14 0.00 0.000E+00 rev / 2.896E+15 0.00 1.052E+05 / co+oh = co2+h 1.400E+05 1.95 -1.347E+03 rev / 1.568E+07 1.95 2.099E+04 / h+o2 = o+oh 1.970E+14 0.00 1.654E+04 rev / 1.555E+13 0.00 4.250E+02 / o+h2 = h+oh 5.080E+04 2.67 6.292E+03 rev / 2.231E+04 2.67 4.197E+03 / o+h2o = oh+oh 2.970E+06 2.02 1.340E+04 rev / 3.013E+05 2.02 -3.850E+03 / oh+h2 = h+h2o 2.160E+08 1.51 3.430E+03 rev / 9.352E+08 1.51 1.858E+04 / hco+m = h+co+m 1.860E+17 -1.00 1.700E+04 rev / 6.467E+13 0.00 -4.420E+02 / h2/2.5/ h2o/12/ co/1.9/ co2/3.8/ h2o2+oh = h2o+ho2 1.000E+12 0.00 0.000E+00 rev / 1.685E+11 0.33 3.146E+04 / DUPLICATE c2h4+o = ch3+hco 1.020E+07 1.88 1.790E+02 rev / 2.851E+08 1.05 3.177E+04 / h+c2h4(+m) = c2h5(+m) 1.081E+12 0.45 1.822E+03 low/1.112E+34 -5.000E+00 4.448E+03/ troe/1.0 1.000E-15 9.500E+01 2.000E+02/ h2/2/ h2o/5/ co/2/ co2/3/ ch3oh(+m) = ch3+oh(+m) 1.900E+16 0.00 9.173E+04 low / 2.95E+44 -7.35 9.546E+04/ troe/0.414 279. 5459./ h2/2/ h2o/16/ co/2/ co2/3/ c2h6+h = c2h5+h2 5.540E+02 3.50 5.167E+03 rev / 1.355E-01 4.06 8.857E+03 / ch3oh+ho2 = ch2oh+h2o2 3.980E+13 0.00 1.940E+04 rev / 3.130E+15 -0.90 1.075E+04 / c2h5+o2 = c2h4+ho2 1.220E+30 -5.76 1.010E+04 rev / 1.259E+30 -5.63 2.231E+04 / c2h6+oh = c2h5+h2o 5.125E+06 2.06 8.550E+02 rev / 1.010E+07 2.06 2.298E+04 / c2h6+o = c2h5+oh 1.130E+14 0.00 7.850E+03 rev / 2.080E+13 0.00 1.272E+04 / ch3+ho2 = ch3o+oh 1.100E+13 0.00 0.000E+00 rev / 4.780E+14 -0.35 2.455E+04 / co+ho2 = co2+oh 3.010E+13 0.00 2.300E+04 rev / 6.435E+15 -0.33 8.461E+04 / ch3+ch3(+m) = c2h6(+m) 9.214E+16 -1.17 6.358E+02 low/1.135E+36 -5.246 1.705E+03/ troe/0.405 1120. 69.6 1.e+15/ h2/2/ h2o/5/ co/2/ co2/3/ h2o+m = h+oh+m 1.837E+27 -3.00 1.226E+05 rev/ 2.250E+22 -2.00 0.000E+00 / h2/2.5/ h2o/12/ co/1.9/ co2/3.8/ h+o2(+m) = ho2(+m) 1.475E+12 0.60 0.000E+00 low/3.500e+16 -4.10E-01 -1.1160E+03 / troe/5.0000E-01 1.0000E-30 1.0000E+30/ h2/2.5/ h2o/12/ co/1.9/ co2/3.8/ co+o(+m) = co2(+m) 1.800E+10 0.00 2.384E+03 low/1.350E+24 -2.788 4191./ h2/2.5/ h2o/12/ co/1.9/ co2/3.8/ co+o2 = co2+o 1.068E-15 7.13 1.332E+04 rev / 9.444E-15 7.13 1.954E+04 / hco+h = co+h2 7.340E+13 0.00 0.000E+00 rev / 4.813E+14 0.00 9.000E+04 / hco+o = co+oh 3.020E+13 0.00 0.000E+00 rev / 8.697E+13 0.00 8.790E+04 / ch2o+m = hco+h+m 6.283E+29 -3.57 9.320E+04 rev / 2.660E+24 -2.57 4.270E+02 / ch2o+oh = hco+h2o 3.430E+09 1.18 -4.470E+02 rev / 1.186E+09 1.18 2.938E+04 / ch2o+h = hco+h2 9.334E+08 1.50 2.976E+03 rev / 7.453E+07 1.50 1.765E+04 / ch2o+o = hco+oh 6.260E+09 1.15 2.260E+03 rev / 2.195E+08 1.15 1.484E+04 / ch3+oh = ch2o+h2 2.250E+13 0.00 4.300E+03 rev / 6.756E+14 0.00 7.603E+04 / ch3+o = ch2o+h 8.000E+13 0.00 0.000E+00 rev / 1.055E+15 0.00 6.963E+04 / ch3+o2 = ch3o+o 1.995E+18 -1.57 2.923E+04 rev / 3.585E+18 -1.59 -1.610E+03 / ch2o+ch3 = hco+ch4 3.636E-06 5.42 9.980E+02 rev / 7.584E-06 5.42 1.615E+04 / hco+ch3 = ch4+co 1.210E+14 0.00 0.000E+00 rev / 2.073E+16 0.00 9.048E+04 / ch3o(+m) = ch2o+h(+m) 5.450E+13 0.00 1.350E+04 low /2.344E+25 -2.7 3.060E+04/ c2h4(+m) = c2h2+h2(+m) 1.800E+13 0.00 7.600E+04 low /1.500E+15 0.0 5.5443E+04/ ho2+o = oh+o2 3.250E+13 0.00 0.000E+00 rev / 7.857E+14 -0.33 5.539E+04 / hco+ho2 = ch2o+o2 2.974E+10 0.33 -3.861E+03 rev / 2.050E+13 0.00 3.895E+04 / ch3o+o2 = ch2o+ho2 5.500E+10 0.00 2.424E+03 rev / 1.318E+09 0.35 3.139E+04 / ch3+ho2 = ch4+o2 3.000E+12 0.00 0.000E+00 rev / 4.314E+15 -0.33 5.796E+04 / hco+o2 = co+ho2 7.580E+12 0.00 4.100E+02 rev / 9.029E+11 0.33 3.293E+04 / ho2+h = oh+oh 7.080E+13 0.00 3.000E+02 rev / 1.352E+14 -0.33 3.957E+04 / ho2+h = h2+o2 1.660E+13 0.00 8.200E+02 rev / 9.138E+14 -0.33 5.830E+04 / ho2+oh = h2o+o2 2.890E+13 0.00 -5.000E+02 rev/ 6.888E+15 -0.33 7.214E+04 / h2o2+o2 = ho2+ho2 5.942E+17 -0.66 5.315E+04 rev/ 4.200E+14 0.00 1.198E+04 / DUPLICATE oh+oh(+m) = h2o2(+m) 1.236E+14 -.37 0.000E+00 low /3.041E+30 -4.63 2049./ troe /0.47 100. 2000. 1.0e+15/ h2/2.5/ h2o/12/ co/1.9/ co2/3.8/ h2o2+h = h2o+oh 2.410E+13 0.00 3.970E+03 rev / 7.750E+12 0.00 7.471E+04 / ch4+ho2 = ch3+h2o2 3.420E+11 0.00 1.929E+04 rev / 3.365E+11 -0.33 2.502E+03 / ch2o+ho2 = hco+h2o2 5.820E-03 4.53 6.557E+03 rev / 1.194E-02 4.20 4.921E+03 / oh+m = o+h+m 3.909E+22 -2.00 1.053E+05 rev / 4.720E+18 -1.00 0.000E+00 / h2/2.5/ h2o/12/ co/1.9/ co2/3.8/ o2+m = o+o+m 6.473E+20 -1.50 1.215E+05 rev/ 6.170E+15 -0.50 0.000E+00 / h2/2.5/ h2o/12/ co/1.9/ co2/3.8/ h2+m = h+h+m 4.570E+19 -1.40 1.044E+05 rev/ 2.423E+15 -0.40 -3.040E+03 / h2/2.5/ h2o/12/ co/1.9/ co2/3.8/ c2h3+h(+m) = c2h4(+m) 6.100E+12 0.27 2.800E+02 low /9.800E+29 -3.86 3.320E+03/ troe /0.782 208. 2663. 6095./ h2/2.5/ h2o/12/ co/1.9/ co2/3.8/ c2h5+c2h3 = c2h4+c2h4 3.000E+12 0.00 0.000E+00 rev/ 4.820E+14 0.00 7.153E+04 / c2h2+h(+m) = c2h3(+m) 3.110E+11 0.58 2.589E+03 low/2.254e40 -7.269 6577./ troe/ 1.0 1.e-15 675. 1.e+15/ h2/2/ h2o/5/ co/2/ co2/3/ c2h4+h = c2h3+h2 8.420E-03 4.62 2.583E+03 rev / 5.723E-01 3.79 3.233E+03 / c2h4+oh = c2h3+h2o 2.050E+13 0.00 5.955E+03 rev / 1.200E+12 0.00 1.400E+04 / c2h3+o2 = c2h2+ho2 5.190E-15 -1.26 3.310E+03 rev / 2.727E-16 -0.93 1.140E+04 / DUPLICATE c2h2+m = c2h+h+m 4.200E+16 0.00 1.070E+05 rev / 7.130E+07 2.08 -2.891E+04 / c2h2+o2 = hcco+oh 2.000E+08 1.50 3.010E+04 rev / 2.232E+05 1.50 2.540E+04 / ch2+o2 = co+h2o 7.280E+19 -2.54 1.809E+03 rev / 8.508E+20 -2.54 1.798E+05 / c2h2+oh = c2h+h2o 3.370E+07 2.00 1.400E+04 rev / 4.671E+03 3.08 6.850E+02 / o+c2h2 = c2h+oh 3.160E+15 -0.60 1.500E+04 rev / 4.443E+10 0.48 -1.557E+04 / c2h2+o = ch2+co 6.120E+06 2.00 1.900E+03 rev / 1.152E+06 2.00 5.257E+04 / c2h+o2 = hco+co 2.410E+12 0.00 0.000E+00 rev / 1.328E+16 -1.08 1.541E+05 / c2h+o = co+ch 1.810E+13 0.00 0.000E+00 rev / 7.478E+16 -1.08 8.213E+04 / ch2+o2 = hco+oh 1.290E+20 -3.30 2.840E+02 rev / 5.310E+19 -3.30 7.317E+04 / ch2+o = co+h+h 5.000E+13 0.00 0.000E+00 rev / 0.000E+00 0.00 0.000E+00 / ch2+h = ch+h2 1.000E+18 -1.56 0.000E+00 rev / 7.026E+17 -1.56 2.990E+03 / ch2+oh = ch+h2o 1.130E+07 2.00 3.000E+03 rev / 3.437E+07 2.00 2.115E+04 / ch2+o2 = co2+h+h 3.290E+21 -3.30 2.868E+03 rev / 0.000E+00 0.00 0.000E+00 / ch+o2 = hco+o 3.300E+13 0.00 0.000E+00 rev / 4.402E+13 0.00 7.199E+04 / ch3oh+oh = ch2oh+h2o 7.100E+06 1.80 -5.960E+02 rev / 3.293E+01 3.46 2.272E+04 / ch3oh+h = ch3o+h2 3.600E+12 0.00 6.095E+03 rev / 7.467E+12 -0.02 7.825E+03 / ch3oh+h = ch2oh+h2 1.440E+13 0.00 6.095E+03 rev / 1.543E+07 1.66 1.425E+04 / ch3oh+ch3 = ch2oh+ch4 3.190E+01 3.17 7.172E+03 rev / 8.927E-04 4.83 1.581E+04 / ch3oh+o = ch2oh+oh 3.880E+05 2.50 3.080E+03 rev / 4.960E+03 2.50 8.781E+03 / ch2oh+o2 = ch2o+ho2 3.810E+06 2.00 1.641E+03 rev / 1.768E+11 0.67 2.418E+04 / ch2oh(+m) = ch2o+h(+m) 2.800E+14 -0.73 3.282E+04 low/6.01E+33 -5.39 3.62E+04/ troe/ 0.96 67.6 1855. 7543./ c2h3+o2 = c2h2+ho2 2.120E-06 6.00 9.484E+03 rev / 1.114E-07 6.33 1.757E+04 / DUPLICATE h2o2+o = oh+ho2 9.550E+06 2.00 3.970E+03 rev / 2.541E+07 1.68 1.985E+04 / c2h2+o = hcco+h 1.430E+07 2.00 1.900E+03 rev / 2.021E+05 2.00 1.331E+04 / c2h2+oh = ch2co+h 3.236E+13 0.00 1.200E+04 rev / 3.194E+14 0.00 3.267E+04 / ch2co+h = ch3+co 1.100E+13 0.00 3.400E+03 rev / 2.400E+12 0.00 4.020E+04 / ch2co+o = ch2+co2 1.750E+12 0.00 1.350E+03 rev / 3.739E+12 0.00 5.369E+04 / ch2+o2 = ch2o+o 3.290E+21 -3.30 2.868E+03 rev / 3.862E+22 -3.30 6.318E+04 / ch2co(+m) = ch2+co(+m) 3.000E+14 0.00 7.098E+04 low/3.6000E+15 0.00 5.9270E+04/ ch2co+o = hcco+oh 1.000E+13 0.00 8.000E+03 rev / 1.432E+10 0.00 -1.255E+03 / ch2co+oh = hcco+h2o 1.000E+13 0.00 2.000E+03 rev / 1.412E+11 0.00 9.995E+03 / ch2co+h = hcco+h2 2.000E+14 0.00 8.000E+03 rev / 6.522E+11 0.00 8.400E+02 / hcco+oh = hco+hco 1.000E+13 0.00 0.000E+00 rev / 4.820E+13 0.00 4.036E+04 / hcco+h = ch2(s)+co 1.100E+14 0.00 0.000E+00 rev / 6.660E+13 0.00 3.926E+04 / hcco+o = h+co+co 8.000E+13 0.00 0.000E+00 rev / 0.000E+00 0.00 0.000E+00 / c2h6+o2 = c2h5+ho2 4.000E+13 0.00 5.090E+04 rev / 3.000E+11 0.00 0.000E+00 / c2h6+ho2 = c2h5+h2o2 1.700E+13 0.00 2.046E+04 rev / 2.500E+11 0.00 6.500E+03 / ch2+o2 = co2+h2 1.010E+21 -3.30 1.508E+03 rev / 3.054E+23 -3.30 1.867E+05 / ch3+c2h3 = ch4+c2h2 3.920E+11 0.00 0.000E+00 rev / 2.962E+13 0.00 6.605E+04 / ch3+c2h5 = ch4+c2h4 1.950E+13 -0.50 0.000E+00 rev / 2.895E+16 -0.70 7.017E+04 / ch3oh+ch2o = ch3o+ch3o 3.835E+13 0.05 8.472E+04 rev / 6.030E+13 0.00 0.000E+00 / ch2o+ch3o = ch3oh+hco 1.150E+11 0.00 1.280E+03 rev / 3.020E+11 0.00 1.816E+04 / ch4+ch3o = ch3+ch3oh 1.570E+11 0.00 8.842E+03 rev / 1.046E+09 0.00 5.000E+04 / c2h6+ch3o = c2h5+ch3oh 3.000E+11 0.00 7.000E+03 rev / 1.714E+10 0.00 5.000E+04 / c2h3+h = c2h2+h2 2.000E+13 0.00 2.500E+03 rev / 1.331E+13 0.00 6.808E+04 / ch3o+ch3oh = ch2oh+ch3oh 3.000E+11 0.00 4.074E+03 rev / 1.549E+05 1.68 1.050E+04 / ch3oh+oh = ch3o+h2o 1.000E+06 2.10 4.967E+02 rev / 8.981E+06 2.08 1.738E+04 / c2h5+h = ch3+ch3 3.610E+13 0.00 0.000E+00 rev / 5.446E+16 -1.03 1.698E+04 / c2h3+o2 = ch2o+hco 1.700E+29 -5.31 6.500E+03 rev / 1.657E+29 -5.31 9.305E+04 / c2h6 = c2h5+h 2.783E+21 -1.56 1.038E+05 rev / 3.610E+13 0.00 0.000E+00 / c2h5oh(+m) = ch2oh+ch3(+m) 5.710E+23 -1.68 9.441E+04 low/3.110E+85 -18.84 1.1310E+05/ troe/ 0.5 550. 825. 6100./ h2/2/ h2o/5/ co/2/ co2/3/ c2h5oh(+m) = c2h5+oh(+m) 2.400E+23 -1.62 9.954E+04 low/5.110E+85 -18.80 1.1877E+05/ troe/ 0.5 650. 800. 1.0E+15/ h2/2/ h2o/5/ co/2/ co2/3/ c2h5oh(+m) = c2h4+h2o(+m) 2.790E+13 0.09 6.614E+04 low/2.570E+83 -18.85 8.6453E+04/ troe/ 0.7 350. 800. 3800./ h2o/5/ c2h5oh(+m) = ch3cho+h2(+m) 7.240E+11 0.10 9.101E+04 low/4.460E+87 -19.42 1.1559E+05/ troe/ 0.9 900. 1100. 3500./ h2o/5/ c2h5oh+o2 = pc2h4oh+ho2 2.000E+13 0.00 5.280E+04 rev / 3.470E+08 0.32 -1.105E+03 / c2h5oh+o2 = sc2h4oh+ho2 1.500E+13 0.00 5.015E+04 rev / 1.079E+09 0.63 -5.040E+02 / c2h5oh+oh = pc2h4oh+h2o 1.740E+11 0.27 6.000E+02 rev / 7.196E+08 0.26 1.933E+04 / c2h5oh+oh = sc2h4oh+h2o 4.640E+11 0.15 0.000E+00 rev / 7.957E+09 0.45 2.199E+04 / c2h5oh+h = pc2h4oh+h2 1.230E+07 1.80 5.098E+03 rev / 1.175E+04 1.79 8.677E+03 / c2h5oh+h = sc2h4oh+h2 2.580E+07 1.65 2.827E+03 rev / 1.022E+05 1.95 9.657E+03 / c2h5oh+ho2 = pc2h4oh+h2o2 1.230E+04 2.55 1.575E+04 rev / 3.019E+02 2.21 3.021E+03 / c2h5oh+ho2 = sc2h4oh+h2o2 8.200E+03 2.55 1.075E+04 rev / 8.348E+02 2.53 1.272E+03 / c2h5oh+ho2 = c2h5o+h2o2 2.500E+12 0.00 2.400E+04 rev / 1.514E+14 -1.80 3.800E+04 / c2h5oh+o = pc2h4oh+oh 9.410E+07 1.70 5.459E+03 rev / 3.947E+04 1.69 6.943E+03 / c2h5oh+o = sc2h4oh+oh 1.880E+07 1.85 1.824E+03 rev / 3.270E+04 2.15 6.559E+03 / c2h5oh+ch3 = pc2h4oh+ch4 1.330E+02 3.18 9.362E+03 rev / 3.319E+00 3.17 1.342E+04 / c2h5oh+ch3 = sc2h4oh+ch4 4.440E+02 2.90 7.690E+03 rev / 4.594E+01 3.20 1.500E+04 / c2h5oh+c2h5 = pc2h4oh+c2h6 5.000E+10 0.00 1.340E+04 rev / 6.995E+10 0.00 2.699E+04 / c2h5oh+c2h5 = sc2h4oh+c2h6 5.000E+10 0.00 1.040E+04 rev / 6.995E+10 0.00 2.399E+00 / pc2h4oh = c2h4+oh 1.293E+12 -0.37 2.685E+04 rev / 9.930E+11 0.00 -9.600E+02 / sc2h4oh+m = ch3cho+h+m 1.000E+14 0.00 2.500E+04 rev / 8.166E+12 0.37 7.300E+02 / c2h4+ch3 = c2h3+ch4 6.620E+00 3.70 9.500E+03 rev / 1.440E+00 4.02 5.472E+03 / ch3co(+m) = ch3+co(+m) 3.000E+12 0.00 1.672E+04 low/1.20E+15 0.00 1.2518E+04/ ch3cho = ch3+hco 2.614E+15 0.15 8.055E+04 rev / 2.000E+13 0.00 0.000E+00 / ch3cho+o2 = ch3co+ho2 3.010E+13 0.00 3.915E+04 rev / 8.552E+10 0.32 -1.940E+03 / ch3cho+oh = ch3co+h2o 2.000E+06 1.80 1.300E+03 rev / 1.354E+06 1.79 3.285E+04 / ch3cho+h = ch3co+h2 1.340E+13 0.00 3.300E+03 rev / 2.096E+12 -0.01 1.969E+04 / ch3cho+o = ch3co+oh 5.940E+12 0.00 1.868E+03 rev / 4.080E+11 -0.01 1.617E+04 / ch3cho+ho2 = ch3co+h2o2 3.010E+12 0.00 1.193E+04 rev / 1.210E+13 -0.34 1.201E+04 / ch3cho+ch3 = ch3co+ch4 2.608E+06 1.78 5.911E+03 rev / 1.066E+07 1.77 2.279E+04 / c2h4+o2 = c2h3+ho2 4.000E+13 0.00 5.820E+04 rev / 4.939E+13 -0.50 1.368E+03 / ch2o+m = co+h2+m 1.826E+32 -4.42 8.712E+04 rev / 5.070E+27 -3.42 8.435E+04 / c2h4+ch3o = c2h3+ch3oh 1.200E+11 0.00 6.750E+03 rev / 1.000E+10 0.00 9.000E+03 / ch3coch3 = ch3co+ch3 1.219E+23 -1.99 8.395E+04 rev / 1.000E+13 0.00 0.000E+00 / ch3coch3+oh = ch3coch2+h2o 1.054E+10 0.97 1.586E+03 rev / 6.931E+09 0.97 2.325E+04 / ch3coch3+h = ch3coch2+h2 5.628E+07 2.00 7.700E+03 rev / 9.000E+12 0.00 1.450E+05 / ch3coch3+o = ch3coch2+oh 1.130E+14 0.00 7.850E+03 rev / 7.500E+12 0.00 1.230E+04 / ch3coch3+ch3 = ch3coch2+ch4 3.960E+11 0.00 9.784E+03 rev / 5.378E+08 0.86 1.754E+04 / ch3coch3+ch3o = ch3coch2+ch3oh 1.000E+11 0.00 7.000E+03 rev / 1.000E+10 0.00 9.000E+03 / ch3coch2 = ch2co+ch3 1.000E+14 0.00 3.100E+04 rev / 1.000E+11 0.00 6.000E+03 / ch3coch3+o2 = ch3coch2+ho2 1.200E+14 0.00 4.600E+04 rev / 2.000E+12 0.00 2.000E+03 / ch3coch3+ho2 = ch3coch2+h2o2 1.700E+13 0.00 2.046E+04 rev / 1.000E+11 0.00 8.000E+03 / c2h5co = c2h5+co 1.834E+15 -0.73 1.291E+04 rev / 1.510E+11 0.00 4.810E+03 / c2h5cho+h = c2h5co+h2 3.980E+13 0.00 4.200E+03 rev / 1.778E+13 0.00 2.367E+04 / c2h5cho+o = c2h5co+oh 5.010E+12 0.00 1.790E+03 rev / 1.000E+12 0.00 1.916E+04 / c2h5cho+oh = c2h5co+h2o 9.240E+06 1.50 -9.620E+02 rev / 5.855E+06 1.50 3.058E+04 / c2h5cho+ch3 = c2h5co+ch4 2.608E+06 1.78 5.911E+03 rev / 9.972E+06 1.78 2.278E+04 / c2h5cho+ho2 = c2h5co+h2o2 1.000E+12 0.00 1.100E+04 rev / 1.000E+12 0.00 1.400E+04 / c2h5cho+ch3o = c2h5co+ch3oh 1.000E+12 0.00 3.300E+03 rev / 3.160E+11 0.00 1.800E+04 / c2h5cho+c2h5 = c2h5co+c2h6 1.000E+12 0.00 8.000E+03 rev / 1.585E+13 0.00 2.800E+04 / c2h5cho = c2h5+hco 9.850E+18 -0.73 8.171E+04 rev / 1.810E+13 0.00 0.000E+00 / c2h5cho+o2 = c2h5co+ho2 2.000E+13 0.50 4.220E+04 rev / 1.909E+14 0.50 3.090E+03 / c2h5cho+c2h3 = c2h5co+c2h4 1.700E+12 0.00 8.440E+03 rev / 2.488E+14 0.00 2.619E+04 / h2o2+h = h2+ho2 4.820E+13 0.00 7.950E+03 rev / 1.875E+12 0.33 2.426E+04 / hco+o = co2+h 3.000E+13 0.00 0.000E+00 rev / 9.677E+15 0.00 1.102E+05 / ch3+m = ch2+h+m 1.968E+16 0.00 9.252E+04 rev / 2.107E+11 1.00 -1.962E+04 / ch3+h = ch2+h2 9.000E+13 0.00 1.510E+04 rev / 1.818E+13 0.00 1.040E+04 / ch3+oh = ch2+h2o 3.000E+06 2.00 2.500E+03 rev / 2.623E+06 2.00 1.296E+04 / ch+ch4 = c2h4+h 6.000E+13 0.00 0.000E+00 rev / 3.573E+14 0.00 5.548E+04 / ch3oh(+m) = ch2oh+h(+m) 2.690E+16 -0.08 9.894E+04 low / 2.34E+40 -6.33 1.031E+05/ troe/ 0.773 693. 5333./ ch3co+h = ch2co+h2 2.000E+13 0.00 1.000E-10 rev / 7.270E+09 0.00 8.304E+04 / ch3co+o = ch2co+oh 2.000E+13 0.00 1.000E-10 rev / 7.270E+09 0.00 8.304E+04 / ch3co+ch3 = ch2co+ch4 5.000E+13 0.00 1.000E-10 rev / 7.270E+09 0.00 8.304E+04 / c2h4+o = ch2cho+h 3.390E+06 1.88 1.790E+02 rev / 9.481E+06 1.79 1.605E+04 / c2h5+o = ch3cho+h 5.000E+13 0.00 0.000E+00 rev / 9.000E+13 0.00 7.268E+04 / c2h6+ch = c2h5+ch2 1.100E+14 0.00 -2.600E+02 rev / 3.829E+10 0.56 4.400E+02 / ch2oh+ch2o=ch3oh+hco 1.292E-01 4.56 6.596E+03 rev / 9.630E+03 2.90 1.311E+04 / c2h5oh+oh = c2h5o+h2o 7.460E+11 0.30 1.634E+03 rev / 3.956E+13 -0.14 1.852E+04 / c2h5oh+h = c2h5o+h2 1.500E+07 1.60 3.038E+03 rev / 1.837E+08 1.17 4.772E+03 / c2h5oh+o = c2h5o+oh 1.580E+07 2.00 4.448E+03 rev / 8.500E+07 1.56 4.087E+03 / c2h5oh+ch3 = c2h5o+ch4 1.340E+02 2.92 7.452E+03 rev / 4.288E+04 2.48 9.666E+03 / sc2h4oh+o2 = ch3cho+ho2 3.810E+06 2.00 1.641E+03 rev / 1.066E+08 1.70 2.733E+04 / c2h5o+o2 = ch3cho+ho2 4.280E+10 0.00 1.097E+03 rev / 3.872E+08 0.44 3.188E+04 / h2o2+o2 = ho2+ho2 1.839E+14 -0.66 3.955E+04 rev / 1.300E+11 0.00 -1.629E+03 / DUPLICATE h2o2+oh = h2o+ho2 5.800E+14 0.00 9.560E+03 rev / 9.771E+13 0.33 4.102E+04 / DUPLICATE c2h5o2 = c2h5+o2 4.930E+50 -11.50 4.225E+04 rev / 1.090E+48 -11.54 1.022E+04 / ch3o2+m = ch3+o2+m 4.343E+27 -3.42 3.047E+04 rev / 5.440E+25 -3.30 0.000E+00 / ch3o2h = ch3o+oh 6.310E+14 0.00 4.230E+04 rev / 1.166E+11 0.60 -1.771E+03 / c2h5o2h = c2h5o+oh 6.310E+14 0.00 4.230E+04 rev / 1.012E+08 1.48 -3.887E+03 / c2h5o+m = ch3+ch2o+m 1.350E+38 -6.96 2.380E+04 rev / 6.442E+36 -6.99 1.685E+04 / ch3o2+ch2o = ch3o2h+hco 1.990E+12 0.00 1.167E+04 rev / 8.504E+12 -0.50 7.009E+03 / c2h5o2+ch2o = c2h5o2h+hco 1.990E+12 0.00 1.167E+04 rev / 6.411E+12 -0.47 6.967E+03 / c2h4+ch3o2 = c2h3+ch3o2h 1.130E+13 0.00 3.043E+04 rev / 3.000E+12 0.00 1.150E+04 / c2h4+c2h5o2 = c2h3+c2h5o2h 1.130E+13 0.00 3.043E+04 rev / 3.000E+12 0.00 1.150E+04 / ch4+ch3o2 = ch3+ch3o2h 1.810E+11 0.00 1.848E+04 rev / 3.708E+11 -0.50 -1.327E+03 / ch4+c2h5o2 = ch3+c2h5o2h 1.810E+11 0.00 1.848E+04 rev / 2.796E+11 -0.47 -1.369E+03 / ch3oh+ch3o2 = ch2oh+ch3o2h 1.810E+12 0.00 1.371E+04 rev / 1.038E+08 1.16 2.542E+03 / ch3oh+c2h5o2 = ch2oh+c2h5o2h 1.810E+12 0.00 1.371E+04 rev / 7.824E+07 1.19 2.500E+03 / c2h5+ho2 = c2h5o+oh 3.200E+13 0.00 0.000E+00 rev / 3.075E+15 -0.32 2.749E+04 / ch3o2+ch3 = ch3o+ch3o 7.000E+12 0.00 -1.000E+03 rev / 2.971E+16 -0.93 2.831E+04 / ch3o2+c2h5 = ch3o+c2h5o 7.000E+12 0.00 -1.000E+03 rev / 6.569E+16 -0.90 3.126E+04 / ch3o2+ho2 = ch3o2h+o2 1.750E+10 0.00 -3.275E+03 rev / 5.156E+13 -0.83 3.488E+04 / ch3oh+o2 = ch2oh+ho2 2.050E+13 0.00 4.490E+04 rev / 3.989E+05 1.99 -4.424E+03 / c2h5o2+ho2 = c2h5o2h+o2 1.750E+10 0.00 -3.275E+03 rev / 3.887E+13 -0.79 3.484E+04 / ch3o2+ch3o2 = ch2o+ch3oh+o2 3.110E+14 -1.61 -1.051E+03 rev / 0.000E+00 0.00 0.000E+00 / ch3o2+ch3o2 = o2+ch3o+ch3o 1.400E+16 -1.61 1.860E+03 rev / 0.000E+00 0.00 0.000E+00 / c2h6+ch3o2 = c2h5+ch3o2h 1.700E+13 0.00 2.046E+04 rev / 7.500E+11 0.00 1.280E+03 / c2h6+c2h5o2 = c2h5+c2h5o2h 1.700E+13 0.00 2.046E+04 rev / 7.500E+11 0.00 1.280E+03 / o2c2h4oh = pc2h4oh+o2 3.900E+16 -1.00 3.000E+04 rev / 1.200E+11 0.00 -1.100E+03 / o2c2h4oh = oh+ch2o+ch2o 1.250E+10 0.00 1.890E+04 rev / 0.000E+00 0.00 0.000E+00 / c2h5o2 = c2h4o2h 5.640E+47 -11.44 3.732E+04 rev / 6.990E+48 -12.22 2.585E+04 / c2h4o2h = c2h4o1-2+oh 4.250E+22 -4.18 2.235E+04 rev / 0.000E+00 0.00 0.000E+00 / ch3co3 = ch3co+o2 4.732E+19 -1.93 2.590E+04 rev / 1.200E+11 0.00 -1.100E+03 / ch3co2+m = ch3+co2+m 4.400E+15 0.00 1.050E+04 rev / 9.648E+12 0.20 2.104E+04 / ch3co3h = ch3co2+oh 5.010E+14 0.00 4.015E+04 rev / 1.738E+08 1.57 1.305E+03 / ch3co3+ho2 = ch3co3h+o2 1.750E+10 0.00 -3.275E+03 rev / 4.000E+12 -0.30 5.270E+04 / c2h5o+m = ch3cho+h+m 1.160E+35 -5.89 2.527E+04 rev / 3.063E+30 -4.78 6.100E+03 / h2o2+ch3co3 = ho2+ch3co3h 2.410E+12 0.00 9.936E+03 rev / 3.894E+11 0.35 2.473E+04 / ch4+ch3co3 = ch3+ch3co3h 1.810E+11 0.00 1.848E+04 rev / 2.877E+10 0.03 1.649E+04 / c2h4+ch3co3 = c2h3+ch3co3h 1.130E+13 0.00 3.043E+04 rev / 3.189E+15 -0.80 2.957E+04 / c2h6+ch3co3 = c2h5+ch3co3h 1.700E+13 0.00 2.046E+04 rev / 1.727E+10 0.59 2.264E+04 / ch2o+ch3co3 = hco+ch3co3h 1.990E+12 0.00 1.167E+04 rev / 6.598E+11 0.03 2.483E+04 / ch3o2+ch3cho = ch3o2h+ch3co 3.010E+12 0.00 1.193E+04 rev / 2.519E+13 -0.51 8.991E+03 / ch3cho+ch3co3 = ch3co+ch3co3h 3.010E+12 0.00 1.193E+04 rev / 1.955E+12 0.02 2.681E+04 / c2h3co = c2h3+co 2.040E+14 -0.40 3.145E+04 rev / 1.510E+11 0.00 4.810E+03 / c2h3cho+oh = c2h3co+h2o 9.240E+06 1.50 -9.620E+02 rev / 1.439E+07 1.53 3.645E+04 / c2h3cho+h = c2h3co+h2 1.340E+13 0.00 3.300E+03 rev / 4.820E+12 0.03 2.556E+04 / c2h3cho+o = c2h3co+oh 5.940E+12 0.00 1.868E+03 rev / 9.384E+11 0.03 2.203E+04 / c2h3cho+ho2 = c2h3co+h2o2 3.010E+12 0.00 1.193E+04 rev / 2.783E+13 -0.30 1.788E+04 / c2h3cho+ch3 = c2h3co+ch4 2.608E+06 1.78 5.911E+03 rev / 2.451E+07 1.81 2.865E+04 / c2h3cho+ch3o2 = c2h3co+ch3o2h 3.010E+12 0.00 1.193E+04 rev / 5.794E+13 -0.48 1.486E+04 / c2h4o2h = c2h4+ho2 9.290E+30 -6.10 1.993E+04 rev / 1.879E+25 -4.48 1.166E+04 / c2h4+ch3o2 = c2h4o1-2+ch3o 2.820E+12 0.00 1.711E+04 rev / 0.000E+00 0.00 0.000E+00 / c2h4+c2h5o2 = c2h4o1-2+c2h5o 2.820E+12 0.00 1.711E+04 rev / 0.000E+00 0.00 0.000E+00 / c2h4o1-2 = ch3+hco 3.630E+13 0.00 5.720E+04 rev / 1.482E+06 1.00 2.420E+02 / c2h4o1-2 = ch3cho 7.407E+12 0.00 5.380E+04 rev / 3.953E+07 1.15 7.739E+04 / c2h4o1-2+oh = c2h3o1-2+h2o 1.780E+13 0.00 3.610E+03 rev / 4.815E+12 -0.98 3.923E+04 / c2h4o1-2+h = c2h3o1-2+h2 8.000E+13 0.00 9.680E+03 rev / 4.998E+12 -0.98 3.014E+04 / c2h4o1-2+ho2 = c2h3o1-2+h2o2 1.130E+13 0.00 3.043E+04 rev / 1.814E+13 -1.30 3.458E+04 / c2h4o1-2+ch3o2 = c2h3o1-2+ch3o2h 1.130E+13 0.00 3.043E+04 rev / 3.778E+13 -1.48 3.156E+04 / c2h4o1-2+c2h5o2 = c2h3o1-2+c2h5o2h 1.130E+13 0.00 3.043E+04 rev / 2.849E+13 -1.44 3.152E+04 / c2h4o1-2+ch3 = c2h3o1-2+ch4 1.070E+12 0.00 1.183E+04 rev / 1.746E+12 -0.98 3.277E+04 / c2h4o1-2+ch3o = c2h3o1-2+ch3oh 1.200E+11 0.00 6.750E+03 rev / 3.614E+09 -0.95 2.548E+04 / ch3coch2o2 = ch3coch2+o2 8.093E+15 -1.11 2.745E+04 rev / 1.200E+11 0.00 -1.100E+03 / ch3coch3+ch3coch2o2 = ch3coch2+ch3coch2o2h 1.000E+11 0.00 5.000E+03 rev / 1.995E+10 0.00 1.000E+04 / ch2o+ch3coch2o2 = hco+ch3coch2o2h 1.288E+11 0.00 9.000E+03 rev / 2.512E+10 0.00 1.010E+04 / ho2+ch3coch2o2 = ch3coch2o2h+o2 1.000E+12 0.00 0.000E+00 rev / 0.000E+00 0.00 0.000E+00 / ch3coch2o2h = ch3coch2o+oh 1.000E+16 0.00 4.300E+04 rev / 9.732E+08 1.70 -4.175E+03 / ch3coch2o = ch3co+ch2o 4.159E+16 -1.03 1.396E+04 rev / 1.000E+11 0.00 1.190E+04 / c2h5cho+ch3o2 = c2h5co+ch3o2h 3.010E+12 0.00 1.193E+04 rev / 2.358E+13 -0.51 8.983E+03 / c2h5cho+c2h5o = c2h5co+c2h5oh 6.026E+11 0.00 3.300E+03 rev / 3.020E+11 0.00 1.816E+04 / c2h5cho+c2h5o2 = c2h5co+c2h5o2h 3.010E+12 0.00 1.193E+04 rev / 1.778E+13 -0.47 8.941E+03 / c2h5cho+ch3co3 = c2h5co+ch3co3h 3.010E+12 0.00 1.193E+04 rev / 1.829E+12 0.02 2.680E+04 / ch3cho+oh = ch3 + hocho 3.000E+15 -1.08 0.000E+00 rev / 5.350E+19 -1.68 1.198E+05 / c2h3o1-2 = ch3co 8.500E+14 0.00 1.400E+04 rev / 1.136E+10 2.11 3.352E+04 / c2h3o1-2 = ch2cho 1.000E+14 0.00 1.400E+04 rev / 1.233E+11 1.71 2.830E+04 / ch2cho = ch2co+h 3.094E+15 -0.26 5.082E+04 rev / 5.000E+13 0.00 1.230E+04 / ch2cho+o2 = ch2o+co+oh 2.000E+13 0.00 4.200E+03 rev / 0.000E+00 0.00 0.000E+00 / hco3 = hco+o2 7.766E+26 -3.96 4.423E+04 rev / 1.200E+11 0.00 -1.100E+03 / ch2o+hco3 = hco+hco3h 1.990E+12 0.00 1.167E+04 rev / 2.331E+02 2.30 4.687E+03 / hco3h = ocho+oh 5.010E+14 0.00 4.015E+04 rev / 2.322E+06 2.15 6.550E+02 / ocho+m = h+co2+m 2.443E+15 -0.50 2.650E+04 rev / 7.500E+13 0.00 2.900E+04 / hcco+o2 = co2+hco 2.400E+11 0.00 -8.540E+02 rev / 1.474E+14 0.00 1.336E+05 / ch3cho+oh = ch2cho + h2o 1.720E+05 2.40 8.150E+02 rev / 6.181E+08 1.25 8.984E+04 / ch2co+oh = ch2oh+co 3.730E+12 0.00 -1.013E+03 rev / 9.430E+06 1.66 2.749E+04 / ch3+o2 = ch2o+oh 7.470E+11 0.00 1.425E+04 rev / 7.778E+11 0.00 6.777E+04 / c2h4+h2 = ch3+ch3 3.767E+12 0.83 8.471E+04 rev / 1.000E+14 0.00 3.200E+04 / ch3+oh = ch2(s)+h2o 2.650E+13 0.00 2.186E+03 rev / 3.236E+10 0.89 1.211E+03 / c2h4+ho2 = c2h4o1-2+oh 2.230E+12 0.00 1.719E+04 rev / 3.518E+17 -1.16 3.967E+04 / ch3och3 = ch3+ch3o 4.860E+55 -11.56 1.021E+05 rev / 1.173E+54 -11.88 2.310E+04 / ch3och3+oh = ch3och2+h2o 9.350E+05 2.29 -7.800E+02 rev / 1.030E+06 1.99 2.329E+04 / ch3och3+h = ch3och2+h2 7.721E+06 2.09 3.384E+03 rev / 1.964E+06 1.79 1.230E+04 / ch3och3+o = ch3och2+oh 1.855E-03 5.29 -1.090E+02 rev / 2.073E-04 5.00 6.708E+03 / ch3och3+ho2 = ch3och2+h2o2 1.680E+13 0.00 1.769E+04 rev / 1.098E+14 -0.62 1.029E+04 / ch3och3+ch3o2 = ch3och2+ch3o2h 1.680E+13 0.00 1.769E+04 rev / 2.287E+14 -0.80 7.270E+03 / ch3och3+ch3 = ch3och2+ch4 1.445E-06 5.73 5.699E+03 rev / 9.603E-06 5.43 1.509E+04 / ch3och3+o2 = ch3och2+ho2 4.100E+13 0.00 4.491E+04 rev / 1.895E+11 0.03 -3.659E+03 / ch3och3+ch3o = ch3och2+ch3oh 6.020E+11 0.00 4.074E+03 rev / 7.383E+10 -0.27 1.026E+04 / ch3och2 = ch2o+ch3 1.600E+13 0.00 2.550E+04 rev / 2.002E+12 0.00 2.400E+04 / ch3och2+ch3o = ch3och3+ch2o 2.410E+13 0.00 0.000E+00 rev / 1.250E+14 0.32 7.854E+04 / ch3och2+ch2o = ch3och3+hco 5.490E+03 2.80 5.862E+03 rev / 1.723E+03 3.10 1.162E+04 / ch3och2+ch3cho = ch3och3+ch3co 1.260E+12 0.00 8.499E+03 rev / 7.746E+11 0.28 1.698E+04 / ch3och2+ho2 = ch3och2o+oh 9.000E+12 0.00 0.000E+00 rev / 2.535E+15 -0.48 3.051E+04 / ch3och2o2 = ch3och2+o2 4.439E+19 -1.59 3.624E+04 rev / 2.000E+12 0.00 0.000E+00 / ch3och3+ch3och2o2 = ch3och2+ch3och2o2h 5.000E+12 0.00 1.769E+04 rev / 6.428E+13 -0.79 7.258E+03 / ch3och2o2+ch2o = ch3och2o2h+hco 1.000E+12 0.00 1.167E+04 rev / 4.035E+12 -0.50 6.997E+03 / ch3och2o2+ch3cho = ch3och2o2h+ch3co 2.800E+12 0.00 1.360E+04 rev / 1.000E+12 0.00 1.000E+04 / ch3och2o2h = ch3och2o+oh 4.384E+21 -1.94 4.387E+04 rev / 2.000E+13 0.00 0.000E+00 / ch3och2o = ch3o+ch2o 5.180E+12 -0.13 1.937E+04 rev / 1.000E+11 0.00 1.190E+04 / ch3och2o2 = ch2och2o2h 6.000E+10 0.00 2.158E+04 rev / 1.248E+12 -0.77 1.122E+04 / ch2och2o2h = oh+ch2o+ch2o 1.500E+13 0.00 2.076E+04 rev / 0.000E+00 0.00 0.000E+00 / o2ch2och2o2h = ch2och2o2h+o2 1.924E+19 -1.62 3.627E+04 rev / 7.000E+11 0.00 0.000E+00 / o2ch2och2o2h = ho2ch2ocho+oh 4.000E+10 0.00 1.858E+04 rev / 7.814E+03 1.49 5.881E+04 / ho2ch2ocho = och2ocho+oh 2.000E+16 0.00 4.050E+04 rev / 1.761E+09 1.49 -3.185E+03 / och2ocho = ch2o+ocho 5.964E+16 -1.50 1.962E+04 rev / 1.250E+11 0.00 1.190E+04 / c2h5o2 = c2h4+ho2 3.370E+55 -13.42 4.467E+04 rev / 1.290E+50 -12.28 2.130E+04 / c2h4o2h = c2h5+o2 2.150E+37 -8.21 2.802E+04 rev / 2.420E+35 -8.03 8.312E+03 / ch3o+ch3 = ch2o+ch4 2.400E+13 0.00 0.000E+00 rev / 8.270E+14 0.02 8.693E+04 / ch3och3+hco3 = ch3och2+hco3h 4.425E+04 2.60 1.391E+04 rev / 1.651E-05 4.61 1.172E+03 / och2ocho = hoch2oco 1.000E+11 0.00 1.400E+04 rev / 2.746E+08 -0.79 2.008E+04 / hoch2oco = hoch2o+co 2.177E+16 -2.69 1.720E+04 rev / 1.500E+11 0.00 4.800E+03 / hoch2oco = ch2oh+co2 8.672E+17 -3.45 1.908E+04 rev / 1.500E+11 0.00 3.520E+04 / ch2oh+ho2 = hoch2o+oh 1.000E+13 0.00 0.000E+00 rev / 8.515E+16 -1.09 3.309E+04 / hoch2o = ch2o+oh 1.482E+17 -1.21 2.124E+04 rev / 4.500E+15 -1.10 0.000E+00 / hoch2o = hocho+h 1.000E+14 0.00 1.490E+04 rev / 5.904E+11 0.64 9.214E+03 / hocho+m = co+h2o+m 2.300E+13 0.00 5.000E+04 rev / 1.422E+10 0.46 4.684E+04 / hocho+m = co2+h2+m 1.500E+16 0.00 5.700E+04 rev / 2.399E+14 0.46 6.102E+04 / ch3och2o2+ch3och2o2 = ch3ocho+ch3och2oh+o2 6.630E+22 -4.50 0.000E+00 rev / 0.000E+00 0.00 0.000E+00 / ch3och2o2+ch3och2o2 = o2+ch3och2o+ch3och2o 1.547E+23 -4.50 0.000E+00 rev / 0.000E+00 0.00 0.000E+00 / ch3och2o = ch3ocho+h 1.745E+16 -0.66 1.172E+04 rev / 1.000E+13 0.00 7.838E+03 / och2o2h = ch2o+ho2 1.278E+18 -1.80 1.046E+04 rev / 1.500E+11 0.00 1.190E+04 / och2o2h = hoch2o2 3.000E+11 0.00 8.600E+03 rev / 4.241E+08 0.95 2.620E+04 / hoch2o2+ho2 = hoch2o2h+o2 3.500E+10 0.00 -3.275E+03 rev / 1.046E+14 -0.84 3.487E+04 / ch3och3+ocho = ch3och2+hocho 1.000E+13 0.00 1.769E+04 rev / 4.884E+12 -0.26 2.508E+04 / hocho = hco+oh 4.593E+18 -0.46 1.083E+05 rev / 1.000E+14 0.00 0.000E+00 / ch2o+ocho = hco+hocho 5.600E+12 0.00 1.360E+04 rev / 8.584E+11 0.04 2.675E+04 / ocho+ho2 = hocho+o2 3.500E+10 0.00 -3.275E+03 rev / 3.699E+12 -0.29 5.269E+04 / ocho+h2o2 = hocho+ho2 2.400E+12 0.00 1.000E+04 rev / 1.793E+11 0.36 2.479E+04 / hocho+oh = h2o+co2+h 2.620E+06 2.06 9.160E+02 rev / 0.000E+00 0.00 0.000E+00 / hocho+oh = h2o+co+oh 1.850E+07 1.51 -9.620E+02 rev / 0.000E+00 0.00 0.000E+00 / hocho+h = h2+co2+h 4.240E+06 2.10 4.868E+03 rev / 0.000E+00 0.00 0.000E+00 / hocho+h = h2+co+oh 6.030E+13 -0.35 2.988E+03 rev / 0.000E+00 0.00 0.000E+00 / hocho+ch3 = ch4+co+oh 3.900E-07 5.80 2.200E+03 rev / 0.000E+00 0.00 0.000E+00 / hocho+ho2 = h2o2+co+oh 1.000E+12 0.00 1.192E+04 rev / 0.000E+00 0.00 0.000E+00 / hocho+o = co+oh+oh 1.770E+18 -1.90 2.975E+03 rev / 0.000E+00 0.00 0.000E+00 / ch2(s)+m = ch2+m 1.000E+13 0.00 0.000E+00 rev / 7.161E+15 -0.89 1.143E+04 / ch2(s)+ch4 = ch3+ch3 4.000E+13 0.00 0.000E+00 rev / 5.429E+15 -0.89 1.565E+04 / ch2(s)+c2h6 = ch3+c2h5 1.200E+14 0.00 0.000E+00 rev / 1.041E+14 -0.33 1.982E+04 / ch2(s)+o2 = co+oh+h 7.000E+13 0.00 0.000E+00 rev / 0.000E+00 0.00 0.000E+00 / ch2(s)+h2 = ch3+h 7.000E+13 0.00 0.000E+00 rev / 2.482E+17 -0.89 1.613E+04 / ch2(s)+h = ch+h2 3.000E+13 0.00 0.000E+00 rev / 1.509E+16 -0.89 1.442E+04 / ch2(s)+o = co+h+h 3.000E+13 0.00 0.000E+00 rev / 0.000E+00 0.00 0.000E+00 / ch2(s)+oh = ch2o+h 3.000E+13 0.00 0.000E+00 rev / 3.194E+18 -0.89 8.786E+04 / ch2(s)+co2 = ch2o+co 3.000E+12 0.00 0.000E+00 rev / 2.852E+15 -0.89 6.552E+04 / ch2(s)+ch3 = c2h4+h 2.000E+13 0.00 0.000E+00 rev / 2.671E+15 -0.06 6.884E+04 / ch2(s)+ch2co = c2h4+co 1.600E+14 0.00 0.000E+00 rev / 4.596E+15 -0.06 1.056E+05 / c2h3+o2 = ch2cho+o 3.500E+14 -0.61 5.260E+03 rev / 2.589E+12 0.12 6.459E+03 / ch3och2och3 = ch3oh+ch3+hco 5.000E+12 0.00 5.500E+04 rev / 0.000E+00 0.00 0.000E+00 / ch3och2och3 = ch3och2+ch3o 2.548E+19 -0.74 8.735E+04 rev / 1.500E+13 0.00 0.000E+00 / ch3och2och3 = ch3och2o+ch3 3.931E+18 -0.61 8.138E+04 rev / 1.500E+13 0.00 0.000E+00 / ch3och2och3+h = ch3och2och2+h2 7.721E+06 2.09 3.384E+03 rev / 1.055E+05 2.22 1.260E+04 / ch3och2och3+h = ch3ochoch3+h2 1.204E+06 2.40 2.580E+03 rev / 5.321E+05 2.22 1.201E+04 / ch3och2och3+o = ch3och2och2+oh 1.855E-03 5.29 -1.090E+02 rev / 1.114E-05 5.42 7.016E+03 / ch3och2och3+o = ch3ochoch3+oh 3.120E+05 2.50 1.113E+03 rev / 6.056E+04 2.32 8.448E+03 / ch3och2och3+oh = ch3och2och2+h2o 9.350E+05 2.29 -7.800E+02 rev / 5.533E+04 2.42 2.360E+04 / ch3och2och3+oh = ch3ochoch3+h2o 3.117E+05 2.29 -7.800E+02 rev / 5.965E+05 2.11 2.380E+04 / ch3och2och3+ch3 = ch3och2och2+ch4 1.445E-06 5.73 5.700E+03 rev / 5.160E-07 5.86 1.540E+04 / ch3och2och3+ch3 = ch3ochoch3+ch4 3.600E-03 4.38 3.500E+03 rev / 4.157E-02 4.20 1.341E+04 / ch3och2och3+ho2 = ch3och2och2+h2o2 1.680E+13 0.00 1.769E+04 rev / 5.902E+12 -0.20 1.060E+04 / ch3och2och3+ho2 = ch3ochoch3+h2o2 5.600E+12 0.00 1.440E+04 rev / 6.361E+13 -0.51 7.522E+03 / ch3och2och3+ch3o2 = ch3och2och2+ch3o2h 1.680E+13 0.00 1.769E+04 rev / 1.229E+13 -0.38 7.578E+03 / ch3och2och3+ch3o2 = ch3ochoch3+ch3o2h 5.600E+12 0.00 1.440E+04 rev / 1.325E+14 -0.69 4.502E+03 / ch3och2och3+o2 = ch3och2och2+ho2 6.000E+13 0.00 4.770E+04 rev / 1.490E+10 0.45 -5.620E+02 / ch3och2och3+o2 = ch3ochoch3+ho2 2.000E+13 0.00 4.420E+04 rev / 1.606E+11 0.14 -3.852E+03 / ch3och2och3+ch3o = ch3och2och2+ch3oh 6.020E+11 0.00 4.074E+03 rev / 3.967E+09 0.15 1.156E+04 / ch3och2och3+ch3o = ch3ochoch3+ch3oh 2.010E+11 0.00 2.873E+03 rev / 4.283E+10 -0.16 1.057E+04 / ch3och2och2 = ch3och2+ch2o 1.760E+15 -0.64 2.202E+04 rev / 1.000E+11 0.00 1.190E+04 / ch3ochoch3 = ch3ocho+ch3 4.195E+16 -0.91 1.052E+04 rev / 1.000E+12 0.00 2.400E+04 / ch3ochoch3 = ch3och2och2 2.400E+12 0.00 3.060E+04 rev / 7.422E+10 0.31 3.039E+04 / ch3och2o+o2 = ch3ocho+ho2 5.000E+10 0.00 5.000E+02 rev / 1.086E+10 -0.02 4.648E+04 / ch3ocho = ch2ocho+h 8.241E+19 -1.15 1.025E+05 rev / 1.000E+14 0.00 0.000E+00 / ch3ocho = ch3oco+h 1.325E+19 -1.00 1.001E+05 rev / 1.000E+14 0.00 0.000E+00 / ch3ocho = ch3oh+co 1.000E+14 0.00 6.250E+04 rev / 1.765E+11 0.03 5.368E+04 / ch3ocho = ch3o+hco 5.374E+16 -0.01 9.709E+04 rev / 3.000E+13 0.00 0.000E+00 / ch3ocho = ch3+ocho 3.214E+17 -0.53 7.997E+04 rev / 1.000E+13 0.00 0.000E+00 / ch3ocho+o2 = ch3oco+ho2 1.000E+13 0.00 4.970E+04 rev / 2.585E+10 0.33 -3.920E+02 / ch3ocho+o2 = ch2ocho+ho2 2.050E+13 0.00 5.200E+04 rev / 8.522E+09 0.48 -5.820E+02 / ch3ocho+oh = ch3oco+h2o 2.340E+07 1.61 -3.500E+01 rev / 1.442E+07 1.61 2.251E+04 / ch3ocho+oh = ch2ocho+h2o 5.270E+09 0.97 1.586E+03 rev / 5.222E+08 1.12 2.164E+04 / ch3ocho+ho2 = ch3oco+h2o2 4.820E+03 2.60 1.391E+04 rev / 1.763E+04 2.28 4.992E+03 / ch3ocho+ho2 = ch2ocho+h2o2 2.380E+04 2.55 1.649E+04 rev / 1.400E+04 2.37 5.086E+03 / ch3ocho+o = ch3oco+oh 2.755E+05 2.45 2.830E+03 rev / 1.722E+04 2.45 8.125E+03 / ch3ocho+o = ch2ocho+oh 9.800E+05 2.43 4.750E+03 rev / 9.850E+03 2.58 7.555E+03 / ch3ocho+h = ch3oco+h2 6.500E+05 2.40 4.471E+03 rev / 9.250E+04 2.40 1.186E+04 / ch3ocho+h = ch2ocho+h2 6.650E+05 2.54 6.756E+03 rev / 1.522E+04 2.69 1.166E+04 / ch3ocho+ch3 = ch3oco+ch4 7.550E-01 3.46 5.481E+03 rev / 2.807E+00 3.46 1.335E+04 / ch3ocho+ch3 = ch2ocho+ch4 4.520E-01 3.65 7.154E+03 rev / 2.702E-01 3.80 1.253E+04 / ch3ocho+ch3o = ch3oco+ch3oh 5.480E+11 0.00 5.000E+03 rev / 3.760E+10 0.03 1.066E+04 / ch3ocho+ch3o = ch2ocho+ch3oh 2.170E+11 0.00 6.458E+03 rev / 2.394E+09 0.18 9.628E+03 / ch3ocho+ch3o2 = ch3oco+ch3o2h 4.820E+03 2.60 1.391E+04 rev / 3.671E+04 2.10 1.972E+03 / ch3ocho+ch3o2 = ch2ocho+ch3o2h 2.380E+04 2.55 1.649E+04 rev / 2.915E+04 2.20 2.066E+03 / ch3ocho+hco = ch3oco+ch2o 5.400E+06 1.90 1.701E+04 rev / 9.624E+06 1.90 9.724E+03 / ch3ocho+hco = ch2ocho+ch2o 1.025E+05 2.50 1.843E+04 rev / 2.938E+04 2.65 8.659E+03 / ch2ocho = ch3oco 2.620E+11 -0.03 3.818E+04 rev / 1.629E+12 -0.18 4.067E+04 / ! ch3oco = ch3+co2 1.185E+12 -0.03 1.262E+04 ! rev / 1.500E+11 0.00 3.520E+04 / ! ch3oco = ch3o+co 5.831E+12 0.00 1.928E+04 ! rev / 1.500E+11 0.00 4.800E+03 / ! ch3oco = ch3+co2 2.33E+11 0.55 1.362E+04 !Glaude 2003: CBSQ+isodesmic rxn+rotor calcs ! ch3oco = ch3o+co 2.50E+12 0.55 2.157E+04 !Glaude 2003: CBSQ+isodesmic rxn+rotor calcs ch3 + co2 = ch3oco 4.76e7 1.54 3.471e4 !Glaude 2003: CBSQ+isodesmic rxn+rotor calcs ch3o + co = ch3oco 1.55e6 2.02 5.734e3 !Glaude 2003: CBSQ+isodesmic rxn+rotor calcs ch2ocho = ch2o+hco 4.661E+12 0.12 2.744E+04 rev / 1.500E+11 0.00 1.190E+04 / amm1oo = ch3oco+o2 9.390E+20 -2.20 4.143E+04 rev / 7.540E+12 0.00 0.000E+00 / ammmoo = ch2ocho+o2 2.428E+21 -2.38 4.028E+04 rev / 4.500E+12 0.00 0.000E+00 / amm1ooh = amm1o+oh 9.450E+15 0.00 4.160E+04 rev / 1.513E+11 1.45 7.825E+03 / ammmooh = ammmo+oh 1.500E+16 0.00 4.250E+04 rev / 8.196E+08 1.75 2.585E+03 / amm1o = co2+ch3o 7.063E+16 -1.19 7.840E+03 rev / 1.000E+11 0.00 9.200E+03 / ammmo = ch2o+ocho 1.376E+17 -1.50 2.419E+04 rev / 1.500E+11 0.00 1.190E+04 / am1oohmoo = amm1oohmj+o2 1.326E+20 -1.72 4.090E+04 rev / 4.520E+12 0.00 0.000E+00 / ammooh1oo = ammmooh1j+o2 1.035E+21 -1.97 4.286E+04 rev / 7.540E+12 0.00 0.000E+00 / ammooh1oo = am1oohm*o+oh 2.894E+10 0.00 2.186E+04 rev / 2.206E+05 1.39 4.596E+04 / amm1oo = amm1oohmj 4.341E+10 0.00 2.460E+04 rev / 1.138E+12 -0.77 1.055E+04 / ammmoo = ammmooh1j 7.679E+10 0.00 2.338E+04 rev / 6.176E+11 -0.49 1.100E+04 / ammcy1om+h = chooco+h2 4.800E+08 1.50 2.005E+03 rev / 2.045E+02 2.75 4.666E+04 / ammcy1om+oh = chooco+h2o 2.400E+06 2.00 -1.192E+03 rev / 4.427E+00 3.25 5.862E+04 / ammcy1om+ho2 = chooco+h2o2 4.000E+12 0.00 1.298E+04 rev / 4.380E+07 0.92 4.133E+04 / amm1oo+h2o2 = amm1ooh+ho2 2.400E+12 0.00 1.000E+04 rev / 3.304E+12 -0.11 6.938E+03 / ammmoo+h2o2 = ammmooh+ho2 2.400E+12 0.00 1.000E+04 rev / 4.114E+12 -0.16 6.878E+03 / amm1oohmj = ammcy1om+oh 7.500E+10 0.00 1.525E+04 rev / 0.000E+00 0.00 0.000E+00 / ammmooh1j = ammcy1om+oh 7.500E+10 0.00 1.525E+04 rev / 0.000E+00 0.00 0.000E+00 / amm1oohmj = ch2o+co2+oh 3.801E+18 -1.47 3.736E+04 rev / 0.000E+00 0.00 0.000E+00 / ammmooh1j = ch2o+co2+oh 9.976E+16 -1.65 2.139E+04 rev / 0.000E+00 0.00 0.000E+00 / ammmooh1j = ch2o+co+ho2 2.078E+16 -1.23 1.767E+04 rev / 0.000E+00 0.00 0.000E+00 / amm1oohmj = ch2o+co+ho2 3.801E+18 -1.47 3.736E+04 rev / 0.000E+00 0.00 0.000E+00 / am1oohm*o = co2+ocho+oh 1.050E+16 0.00 4.160E+04 rev / 0.000E+00 0.00 0.000E+00 / amm1oo+ch3o2 = amm1o+ch3o+o2 1.400E+16 -1.61 1.860E+03 rev / 0.000E+00 0.00 0.000E+00 / ammmoo+ch3o2 = ammmo+ch3o+o2 1.400E+16 -1.61 1.860E+03 rev / 0.000E+00 0.00 0.000E+00 / amm1oo+amm1oo = o2+amm1o+amm1o 1.400E+16 -1.61 1.860E+03 rev / 0.000E+00 0.00 0.000E+00 / ammmoo+ammmoo = o2+ammmo+ammmo 1.400E+16 -1.61 1.860E+03 rev / 0.000E+00 0.00 0.000E+00 / amm1oo+ammmoo = o2+amm1o+ammmo 1.400E+16 -1.61 1.860E+03 rev / 0.000E+00 0.00 0.000E+00 / chooco = ocho+co 7.371E+15 -1.38 1.420E+04 rev / 1.500E+11 0.00 3.000E+03 / chooco = hco+co2 8.348E+13 -0.88 2.799E+04 rev / 1.500E+11 0.00 3.673E+04 / ! Dimethylcarbonate reactions ! Initiation !coc*ooc = ch3och3 + co2 2.39E+12 0.19 69800. ! Ea from CBSQ (Glaude, 5/2003), mtbe+ic4h8+ch3oh X 1/9 ! because MTBE has 9 possible 4 membered TSTs (9 H atoms) ! where in this case only TST can form. ! TST ties up 3 rotors not 2 so correct rate const: coc*ooc = ch3och3 + co2 5.0E+11 0.19 69800.0 ! Ea from CBSQ (Glaude, 5/2003), assume T^0.19 as in mtbe=ic4h8+ch3oh ! (Chiung Ju Chen and Bozzelli). Use A-factor at 298K the same as cc(c)cccc.=>cc(c)c.ccc ! (Viskolcz et al JPC A 101 7119-7127 (1997) which ties up 3 rotors as in the case. Use Afactor at 298K the same as cc(c)ccc.=>cc(c)c.ccc (Viskolcz et al JPC A 101 7119-7127 (1997) which ties up 3 rotors as in the case. coc*ooc + o2 = coc*oocj + ho2 4.2E+13 0.00 5.35E+04 ! Afactor = 7.0e12 per H-atm, Ea=internal energy change of rxn (ic8 paper, C&F) coc*oocj + h = coc*ooc 5.0E+13 0.0 0.0 ! Analogy with H + primary alkyl radical, Curran et al, Iso-octane, C&F 129:253-280 (2002) ch3oco + ch3o = coc*ooc 3.0E+13 0.0 0.0 ! Assumed the same as high pressure rate for ch3o+ch3=>ch3och3 from Fischer et al., ! Dimethyl Ether, IJCK 32:713–740 (2000). coc*ooj + ch3 = coc*ooc 3.0E+13 0.0 0.0 ! Assumed the same as high pressure rate for ch3o+ch3=>ch3och3 from Fischer et al., ! Dimethyl Ether, IJCK 32:713–740 (2000). ! H-atom Abstraction coc*ooc + oh = coc*oocj + h2o 7.02E+07 1.61 -35.0 ! Asume rate rule for secondary from Curran et al, n-heptane, C&F 114:149 (1998) coc*ooc + h = coc*oocj + h2 9.75E+05 2.4 4471.0 ! Assume rate rule for secondary from nc7_38 LLNL mech coc*ooc + ch3 = coc*oocj + ch4 4.06E+04 2.26 7287.0 ! Assume rate rule for secondary from nc7_38 LLNL mech coc*ooc + o = coc*oocj + oh 7.16E+04 2.71 2.11E+03 ! Assume rate rule for secondary from nc7_38 LLNL mech coc*ooc + ho2 = coc*oocj + h2o2 8.40E+12 0.0 1.77E+04 ! Assumed rate rule for secondary from Curran et al, iso-octane, C&F 2002 coc*ooc + ch3o2 = coc*oocj + ch3o2h 8.40E+12 0.0 1.77E+04 ! Assumed rate rule for secondary from Curran et al, iso-octane, C&F 2002 coc*ooc + ch3o = coc*oocj + ch3oh 3.16E+11 0.0 7.00E+03 ! Rate rule for primary from Curran et al, n-heptane, C&F 114:149 (1998) coc*ooc + c2h3 = coc*oocj + c2h4 1.00E+12 0.0 1.80E+04 ! Rate rule for primary from Curran et al, n-heptane, C&F 114:149 (1998) coc*ooc + c2h5 = coc*oocj + c2h6 1.00E+11 0.0 1.34E+04 ! Rate rule for primary from Curran et al, n-heptane, C&F 114:149 (1998) ! radical addition ! For the next two reactions assume chemically activated reaction where stabilization is neglible and reverse reaction ! rate from adduct to reactants is much less than rate from adduct to products. coc*ooc + h => coc*ooh + ch3 3.79E+16 -1.39 5402.0 ! Analogy with ch2o+h=ch2oh, Held and Dryer, IJCK, 30, 805 (1998). !WJP: Eliminate coc*ooc + h => ch3ocho + ch3o This step is endothermic by 2 kcal and would have significant back reaction ! due to exit barrier being 10.8 kcal about the entrance channel. ! coc*ooc + h => ch3ocho + ch3o 4.76E+09 1.02 5181.0 ! Analogy with ch2o+h=ch3o, reverse rate from Hippler, Striebel, and Viskolcz, ! PCCP 3:2450-2458 (2001). ! ! Forward rate is from thermo using cdat 195 ! consumption of coc*ooh !The BD cjoc*ooh is about 100.3 and primary bd is 101 => assume abstraction rates for primary c-h bond: coc*ooh + oh = cjoc*ooh + h2o 5.25E+09 0.97 1590.0 ! Rate rule for primary from Curran et al, n-heptane, C&F 114:149 (1998) coc*ooh + h = cjoc*ooh + h2 9.40E+04 2.75 6280.0 ! Rate rule for primary from nc7_38 LLNL mech coc*ooh + ch3 = cjoc*ooh + ch4 4.52E-01 3.65 7154.0 ! Rate rule for primary from nc7_38 LLNL mech coc*ooh + o = cjoc*ooh + oh 9.65E+04 2.68 3716.0 ! Rate rule for primary from nc7_38 LLNL mech ! Consumption of cjoc*ooh: cjoc*ooh => ch2o + co + oh 6.10E+21 -2.40 3.252e4 ! Analogy with ch2o+hco=ch2ocho, rate from reaction rate rule: anc7, ! "alk" to terminal C in C=O (Betta Fisher, 1999). ! Rate calculated from hoco+ch2o=cjoc*ooh and thermo. Assume hoco has a short lifetime. ! Consumption of radicals formed from DMC: ch3oco + ch2o = coc*oocj 1.06E+11 0.0 7350.0 ! Analogy with ch3co+c2h4=ch2ch2coch3, Curran et al. C&F, iso-octane, 2002, ! divide A-factor by 2 because ! radical can add to only one side of double bond ch3o + co2 = coc*ooj 1.000E+11 0.00 9.20E+03! rule from mbrev mech, reaction class 27 since reaction is uphill, ! use deltahreac+9200 cal as EA; use A from nc descr. of nc7 ! (9200 is EA for typical alkyl addition to internal C, ! which is a downhill reaction). end