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 * **** * **** * **** (DETCHEM format) * **** * *********************************************************************** STICK CH4 +(a) +(b) >CH3(a) +H(b) 4.582E-02 -0.001 33.155 CH3(a) +H(b) >CH4 +(a) +(b) 1.034E+21 0.003 106.180 STICK CH4 +OH(a) +(a) >CH3(a) +H2O(a) 1.510E-02 0.001 28.860 CH3(a) +H2O(a) >CH4 +(a) +OH(a) 7.071E+19 -0.004 104.259 STICK CH4 +O(a) +(a) >CH3(a) +OH(a) 3.082E-02 0.007 26.234 CH3(a) +OH(a) >(a) +O(a) +CH4 2.695E+20 -0.029 192.865 STICK (a) +O2 >O2(a) 5.710E-02 0.000 0.000 O2(a) >(a) +O2 6.702E+15 -0.031 63.541 STICK vac(b) +O2 >O(b) 5.710E-02 0.000 0.000 O(b) >vac(b) +O2 7.024E+15 -0.027 159.975 STICK (a) +O(a) +H2O >OH(a) +OH(a) 1.400E-01 0.000 0.000 OH(a) +OH(a) >(a) +O(a) +H2O 3.307E+21 0.013 191.178 STICK (a) +H2O >H2O(a) 1.400E-01 0.000 0.000 H2O(a) >(a) +H2O 6.293E+12 0.045 99.946 STICK (a) +CO2 >CO2(a) 4.910E-02 0.000 0.000 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) >CH2(b) +OH(a) 1.250E+22 0.012 33.366 CH2(b) +OH(a) >O(a) +CH3(b) 1.855E+22 -0.012 303.074 CH3(b) +OH(a) >H2O(a) +CH2(b) 1.398E+22 -0.004 33.193 H2O(a) +CH2(b) >CH3(b) +OH(a) 1.111E+22 0.004 211.667 CH3(a) +O(a) >(a) +CH2OH(a) 3.534E+21 0.016 30.953 (a) +CH2OH(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) >(a) +CH2OH(a) 3.420E+21 -0.004 12.581 (a) +CH2OH(a)>CH2(a) +OH(a) 2.191E+22 0.004 180.219 (b) +CH2OH(a)>CH2O(a) +H(b) 1.917E+22 0.012 12.654 CH2O(a) +H(b) >(b) +CH2OH(a) 3.348E+20 -0.012 57.646 CH2O(a) +OH(a) >H2O(a) +CHO(a) 5.608E+21 0.012 51.570 H2O(a) +CHO(a) >CH2O(a) +OH(a) 2.119E+22 -0.012 192.230 OH(a) +CHO(a) >CO(a) +H2O(a) 5.921E+22 0.008 65.968 CO(a) +H2O(a) >OH(a) +CHO(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 (b) +CH(a) >vac(b) +CHO(a) 2.103E+21 0.008 24.821 vac(b) +CHO(a) >(b) +CH(a) 1.218E+21 -0.008 215.219 (a) +CH2(b) >vac(b) +CH2O(a) 2.155E+22 0.008 91.222 vac(b) +CH2O(a) >(a) +CH2(b) 2.425E+20 -0.008 9.038 (b) +CH2O(a) >H(b) +CHO(a) 3.274E+21 0.008 69.676 H(b) +CHO(a) >(b) +CH2O(a) 5.962E+22 -0.008 207.964 (b) +CHO(a) >CO(a) +H(b) 1.088E+23 0.004 55.610 CO(a) +H(b) >(b) +CHO(a) 7.956E+22 -0.004 254.800 (b) +CHO(a) >(a) +CHO(b) 2.746E+22 0.018 76.549 (a) +CHO(b) >(b) +CHO(a) 6.754E+21 -0.018 106.611 (a) +CHO(b) >CO(b) +H(a) 2.732E+21 -0.002 141.937 CO(b) +H(a) >(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) >vac(b) +CO2(a) 1.410E+21 0.010 42.023 vac(b) +CO2(a) >(a) +CO(b) 9.554E+20 -0.010 78.477 (a) +H(b) >vac(b) +OH(a) 1.886E+22 0.000 137.800 vac(b) +OH(a) >(a) +H(b) 4.222E+21 0.000 27.900 (a) +O2(a) >O(a) +O(a) 3.815E+22 0.005 174.961 O(a) +O(a) >(a) +O2(a) 1.744E+21 -0.005 59.139 (a) +O(b) >(b) +O(a) 2.380E+22 0.027 116.625 (b) +O(a) >(a) +O(b) 1.797E+21 -0.027 107.875 vac(b) +O(a) >(a) +(b) 8.012E+21 0.020 48.597 (a) +(b) >vac(b) +O(a) 1.387E+22 -0.020 252.103 vac(b) +O2(a) >(b) +O(a) 1.196E+24 0.025 81.408 (b) +O(a) >vac(b) +O2(a) 9.469E+22 -0.025 169.092 (a) +H(b) >(b) +H(a) 6.133E+22 0.002 148.173 (b) +H(a) >(a) +H(b) 9.505E+21 -0.002 117.827 CHO(b) +OH(a) >H2O(a) +CO(b) 2.992E+22 0.001 2.168 H2O(a) +CO(b) >CHO(b) +OH(a) 3.113E+22 -0.001 156.062 (a) +CHO(b) >vac(b) +HCOO(a) 3.658E+21 0.000 11.580 vac(b) +HCOO(a) >(a) +CHO(b) 1.210E+21 0.000 8.680 HCOO(a) +OH(a) >H2O(a) +CO2(a) 2.305E+23 0.011 183.191 H2O(a) +CO2(a) >HCOO(a) +OH(a) 4.912E+23 -0.011 376.439 (b) +HCOO(a) >H(b) +CO2(a) 1.681E+23 0.007 177.623 H(b) +CO2(a) >(b) +HCOO(a) 1.726E+24 -0.007 368.497 H2O(a) +(b) =H(b) +OH(a) 3.659E+21 0.000 12.500 END