!SURFACE MECHANISM FOR OXIDATION OF CH4 OVER PALLADIUM OXIDE !*********************************************************************** !**** * !**** CH4/O2 OVER PDO - SURFACE MECHANISM * !**** thermodynamically consistent (300 - 1073K) * !**** * !**** H. STOTZ, L. MAIER, O. DEUTSCHMANN * !**** KIT (Karlsruhe Institute of Technology) * !**** * !**** References: * !**** H. Stotz, L. Maier, A. Boubnov, A. T. Gremminger, * !**** J.-D. Grunwaldt, O. Deutschmann. Journal of Catalysis * !**** 370 (2019) 152-175. * !**** www.detchem.com/mechanisms * !**** KIT (Karlsruhe Institute of Technology) * !**** Contact: mail@detchem.com (O. Deutschmann) * !**** www.detchem.com/mechanisms * !**** * !**** * !**** Kinetic data: * !**** k = A * T**b * exp (-Ea/RT) A b Ea * !**** (cm,mol,s) - kJ/mol * !**** * !**** STICK: A in next reaction is initial sticking coefficient * !**** * !**** * !**** (CHEMKIN format) * !**** * !*********************************************************************** SITE/(b)_surface/ SDEN/3.554E-09/ (b) vac(b) O(b) H(b) CO(b) CH2(b) CH3(b) CHO(b) END SITE/(a)_surface/ SDEN/3.554E-09/ (a) O(a) O2(a) OH(a) H2O(a) CO(a) H2(a) H(a) CO2(a) CH3(a) CH2OH(a) CH2O(a) CHO(a) CH2(a) CH(a) HCOO(a) END REACTIONS KJOULES/MOLE MWOFF CH4 + (b) + (a) => CH3(a) + H(b) 4.582E-02 -0.001 33.155 STICK CH3(a) + H(b) => (a) + (b) + CH4 1.034E+21 0.003 106.180 CH4 + (a) + OH(a) => CH3(a) + H2O(a) 1.510E-02 0.001 28.860 STICK CH3(a) + H2O(a) => OH(a) + (a) + CH4 7.071E+19 -0.004 104.259 CH4 + (a) + O(a) => CH3(a) + OH(a) 3.082E-02 0.007 26.234 STICK CH3(a) + OH(a) => O(a) + (a) + CH4 2.695E+20 -0.029 192.865 O2 + (a) => O2(a) 5.710E-02 0.000 0.000 STICK O2(a) => (a) + O2 6.702E+15 -0.031 63.541 O2 + vac(b) => O(b) 5.710E-02 0.000 0.000 STICK O(b) => vac(b) + O2 7.024E+15 -0.027 159.975 H2O + (a) + O(a) => OH(a) + OH(a) 1.400E-01 0.000 0.000 STICK OH(a) + OH(a) => O(a) + (a) + H2O 3.307E+21 0.013 191.178 H2O + (a) => H2O(a) 1.400E-01 0.000 0.000 STICK H2O(a) => (a) + H2O 6.293E+12 0.045 99.946 CO2 + (a) => CO2(a) 4.910E-02 0.000 0.000 STICK CO2(a) => (a) + CO2 4.087E+14 0.029 65.097 CH3(a) + (b) => (a) + CH3(b) 1.494E+22 0.008 131.139 (a) + CH3(b) => CH3(a) + (b) 2.441E+23 -0.008 181.201 O(a) + CH3(b) => OH(a) + CH2(b) 1.250E+22 0.012 33.366 OH(a) + CH2(b) => O(a) + CH3(b) 1.855E+22 -0.012 303.074 OH(a) + CH3(b) => H2O(a) + CH2(b) 1.398E+22 -0.004 33.193 H2O(a) + CH2(b) => OH(a) + CH3(b) 1.111E+22 0.004 211.667 CH3(a) + O(a) => CH2OH(a) + (a) 3.534E+21 0.016 30.953 CH2OH(a) + (a) => CH3(a) + O(a) 2.466E+23 -0.016 333.447 CH3(a) + OH(a) => CH2(a) + H2O(a) 2.014E+21 0.004 73.229 CH2(a) + H2O(a) => CH3(a) + OH(a) 1.175E+22 -0.004 116.851 CH2(a) + OH(a) => CH2OH(a) + (a) 3.420E+21 -0.004 12.581 CH2OH(a) + (a) => CH2(a) + OH(a) 2.191E+22 0.004 180.219 CH2OH(a) + (b) => CH2O(a) + H(b) 1.917E+22 0.012 12.654 CH2O(a) + H(b) => CH2OH(a) + (b) 3.348E+20 -0.012 57.646 CH2O(a) + OH(a) => CHO(a) + H2O(a) 5.608E+21 0.012 51.570 CHO(a) + H2O(a) => CH2O(a) + OH(a) 2.119E+22 -0.012 192.230 CHO(a) + OH(a) => CO(a) + H2O(a) 5.921E+22 0.008 65.968 CO(a) + H2O(a) => CHO(a) + OH(a) 8.990E+21 -0.008 267.532 CH3(a) + (b) => CH2(a) + H(b) 1.827E+21 0.000 123.976 CH2(a) + H(b) => CH3(a) + (b) 5.137E+22 -0.000 165.224 CH2(a) + (b) => (a) + CH2(b) 1.257E+22 0.000 13.103 (a) + CH2(b) => CH2(a) + (b) 2.797E+22 -0.000 198.017 CH2(a) + (b) => CH(a) + H(b) 3.793E+22 0.008 112.541 CH(a) + H(b) => CH2(a) + (b) 2.987E+22 -0.008 163.159 CH(a) + (b) => CHO(a) + vac(b) 2.103E+21 0.008 24.821 CHO(a) + vac(b) => CH(a) + (b) 1.218E+21 -0.008 215.219 (a) + CH2(b) => CH2O(a) + vac(b) 2.155E+22 0.008 91.222 CH2O(a) + vac(b) => (a) + CH2(b) 2.425E+20 -0.008 9.038 CH2O(a) + (b) => CHO(a) + H(b) 3.274E+21 0.008 69.676 CHO(a) + H(b) => CH2O(a) + (b) 5.962E+22 -0.008 207.964 CHO(a) + (b) => CO(a) + H(b) 1.088E+23 0.004 55.610 CO(a) + H(b) => CHO(a) + (b) 7.956E+22 -0.004 254.800 CHO(a) + (b) => (a) + CHO(b) 2.746E+22 0.018 76.549 (a) + CHO(b) => CHO(a) + (b) 6.754E+21 -0.018 106.611 (a) + CHO(b) => H(a) + CO(b) 2.732E+21 -0.002 141.937 H(a) + CO(b) => (a) + CHO(b) 2.123E+21 0.002 263.113 CO(a) + (b) => (a) + CO(b) 1.313E+21 0.011 33.868 (a) + CO(b) => CO(a) + (b) 2.212E+21 -0.011 16.262 (a) + CO(b) => CO2(a) + vac(b) 1.410E+21 0.010 42.023 CO2(a) + vac(b) => (a) + CO(b) 9.554E+20 -0.010 78.477 (a) + H(b) => OH(a) + vac(b) 1.886E+22 0.000 137.800 OH(a) + vac(b) => (a) + H(b) 4.222E+21 0.000 27.900 O2(a) + (a) => O(a) + O(a) 3.815E+22 0.005 174.961 O(a) + O(a) => O2(a) + (a) 1.744E+21 -0.005 59.139 (a) + O(b) => O(a) + (b) 2.380E+22 0.027 116.625 O(a) + (b) => (a) + O(b) 1.797E+21 -0.027 107.875 O(a) + vac(b) => (a) + (b) 8.012E+21 0.020 48.597 (a) + (b) => O(a) + vac(b) 1.387E+22 -0.020 252.103 O2(a) + vac(b) => O(a) + (b) 1.196E+24 0.025 81.408 O(a) + (b) => O2(a) + vac(b) 9.469E+22 -0.025 169.092 (a) + H(b) => H(a) + (b) 6.133E+22 0.002 148.173 H(a) + (b) => (a) + H(b) 9.505E+21 -0.002 117.827 OH(a) + CHO(b) => H2O(a) + CO(b) 2.992E+22 0.001 2.168 H2O(a) + CO(b) => OH(a) + CHO(b) 3.113E+22 -0.001 156.062 (a) + CHO(b) => HCOO(a) + vac(b) 3.658E+21 0.000 11.580 HCOO(a) + vac(b) => (a) + CHO(b) 1.210E+21 0.000 8.680 HCOO(a) + OH(a) => CO2(a) + H2O(a) 2.305E+23 0.011 183.191 CO2(a) + H2O(a) => HCOO(a) + OH(a) 4.912E+23 -0.011 376.439 HCOO(a) + (b) => CO2(a) + H(b) 1.681E+23 0.007 177.623 CO2(a) + H(b) => HCOO(a) + (b) 1.726E+24 -0.007 368.497 H2O(a) + (b) <=> OH(a) + H(b) 3.659E+21 0.000 12.500 END