SURFACE MECHANISM FOR OXIDATION OF CH4 OVER REDUCED PALLADIUM *********************************************************************** **** * **** CH4/O2 OVER REDUCED PD - SURFACE MECHANISM * **** thermodynamically consistent (300 - 1400K) * **** * **** H. STOTZ, L. MAIER, O. DEUTSCHMANN * **** KIT (Karlsruhe Institute of Technology) * **** * **** References: * **** H. Stotz, L. Maier, O. Deutschmann * **** Topics in Catalysis: * **** Catalysis and environmental protection, accepted (2016) * **** 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) * **** * *********************************************************************** SURFACE MECHANISM STICK Pd(s) +Pd(s) +H2 >H(s) +H(s) 2.445E-01 -0.076 0.000 STICK Pd(s) +Pd(s) +O2 >O(s) +O(s) 5.712E-02 0.012 1.945 STICK CH4 +Pd(s) >CH4(s) 8.557E-03 0.017 0.000 STICK Pd(s) +H2O >H2O(s) 1.402E-01 0.033 0.000 STICK Pd(s) +CO2 >CO2(s) 8.186E-03 -0.037 0.000 STICK CO +Pd(s) >CO(s) 6.716E-01 0.015 0.935 STICK CH4 +O(s) +O(s) >OH(s) +H3CO(s) 8.928E-03 0.004 159.978 $O(s) 0.000 22.500 H(s) +H(s) >Pd(s) +Pd(s) +H2 8.393E+19 0.303 85.036 O(s) +O(s) >Pd(s) +Pd(s) +O2 2.932E+22 -0.049 221.818 $O(s) 0.000 22.500 H2O(s) >Pd(s) +H2O 1.244E+14 -0.134 46.593 CO(s) >CO +Pd(s) 8.565E+13 -0.062 138.558 $CO(s) 0.000 31.000 CO2(s) >Pd(s) +CO2 1.392E+12 0.146 23.156 CH4(s) >Pd(s) +CH4 1.865E+13 -0.068 29.499 OH(s) +H3CO(s) >CH4 +O(s) +O(s) 2.046E+18 -0.017 248.686 H(s) +O(s) >Pd(s) +OH(s) 3.598E+22 -0.060 85.044 $O(s) 0.000 11.250 Pd(s) +OH(s) >H(s) +O(s) 4.169E+20 0.060 66.456 H(s) +OH(s) >Pd(s) +H2O(s) 3.017E+20 -0.059 -0.823 Pd(s) +H2O(s) >H(s) +OH(s) 4.972E+22 0.059 109.623 OH(s) +OH(s) >O(s) +H2O(s) 2.516E+19 0.001 54.533 O(s) +H2O(s) >OH(s) +OH(s) 3.578E+23 -0.001 183.567 $O(s) 0.000 11.250 C(s) +O(s) >Pd(s) +CO(s) 5.434E+23 0.004 21.097 $O(s) 0.000 11.250 Pd(s) +CO(s) >C(s) +O(s) 2.392E+21 -0.004 214.903 $CO(s) 0.000 31.000 O(s) +CO(s) >CO2(s) +Pd(s) 6.874E+18 0.052 71.247 $O(s) 0.000 11.250 $CO(s) 0.000 31.000 CO2(s) +Pd(s) >O(s) +CO(s) 2.400E+21 -0.052 132.753 CH4(s) +Pd(s) >H(s) +CH3(s) 1.301E+22 0.064 66.978 H(s) +CH3(s) >CH4(s) +Pd(s) 1.052E+21 -0.064 38.422 Pd(s) +CH3(s) >H(s) +CH2(s) 2.811E+24 0.064 104.253 H(s) +CH2(s) >Pd(s) +CH3(s) 4.871E+21 -0.064 37.147 Pd(s) +CH2(s) >H(s) +CH(s) 8.888E+23 0.064 100.278 H(s) +CH(s) >Pd(s) +CH2(s) 1.540E+25 -0.064 63.722 Pd(s) +CH(s) >H(s) +C(s) 2.811E+23 0.064 20.753 H(s) +C(s) >Pd(s) +CH(s) 4.871E+24 -0.064 165.847 CH4(s) +O(s) >OH(s) +CH3(s) 2.591E+24 0.004 96.622 $O(s) 0.000 11.250 OH(s) +CH3(s) >CH4(s) +O(s) 2.427E+21 -0.004 49.478 O(s) +CH3(s) >CH2(s) +OH(s) 2.611E+25 0.004 97.347 $O(s) 0.000 11.250 CH2(s) +OH(s) >O(s) +CH3(s) 5.243E+20 -0.004 11.653 CH2(s) +O(s) >OH(s) +CH(s) 8.257E+21 0.004 88.322 $O(s) 0.000 11.250 OH(s) +CH(s) >CH2(s) +O(s) 1.658E+21 -0.004 33.178 O(s) +CH(s) >C(s) +OH(s) 2.611E+21 0.004 36.847 $O(s) 0.000 11.250 C(s) +OH(s) >O(s) +CH(s) 5.243E+20 -0.004 163.353 C(s) +OH(s) >H(s) +CO(s) 1.898E+22 0.064 0.503 H(s) +CO(s) >C(s) +OH(s) 7.213E+21 -0.064 212.897 $CO(s) 0.000 31.000 O(s) +H3CO(s) >H2CO(s) +OH(s) 2.351E+24 0.017 65.714 $O(s) 0.000 11.250 H2CO(s) +OH(s) >O(s) +H3CO(s) 5.824E+21 -0.017 56.886 H2CO(s) +O(s) >OH(s) +HCO(s) 2.351E+24 0.017 31.014 $O(s) 0.000 11.250 OH(s) +HCO(s) >H2CO(s) +O(s) 5.824E+21 -0.017 14.986 O(s) +HCO(s) >OH(s) +CO(s) 2.351E+24 0.017 12.114 $O(s) 0.000 11.250 OH(s) +CO(s) >O(s) +HCO(s) 5.824E+21 -0.017 111.186 $CO(s) 0.000 31.000 OH(s) +CO(s) >Pd(s) +COOH(s) 4.167E+19 0.018 46.493 $CO(s) 0.000 31.000 Pd(s) +COOH(s) >OH(s) +CO(s) 3.251E+21 -0.018 27.807 Pd(s) +COOH(s) >CO2(s) +H(s) 1.871E+19 0.094 27.009 CO2(s) +H(s) >Pd(s) +COOH(s) 7.228E+21 -0.094 125.791 H(s) +COOH(s) >H2O(s) +CO(s) 2.532E+18 -0.076 61.084 H2O(s) +CO(s) >H(s) +COOH(s) 5.349E+18 0.076 190.216 $CO(s) 0.000 31.000 END