!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) * !**** * !*********************************************************************** SITE/Pd_surface/ SDEN/2.09E-9/ Pd(s) H2O(s) H(s) OH(s) CO(s) C(s) CH3(s) CH2(s) CH(s) CH4(s) O(s) CO2(s) COOH(s) H3CO(s) H2CO(s) HCO(s) END ! THERMO 300.0 1000.0 3000.0 ! all data are dummy data (they are not needed - all rxns irrev.) Pd(s) PD 1 0 0 0 300.00 3000.00 1000.00 1 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 2 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 3 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 4 H2O(s) H 2O 1PD 1 0 300.00 3000.00 1000.00 1 0.41886795E+01 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 2 -0.36246203E+05-0.15678016E+02 0.41886795E+01 0.00000000E+00 0.00000000E+00 3 0.00000000E+00 0.00000000E+00-0.36246203E+05-0.15678016E+02 4 H(s) H 1PD 1 0 0 300.00 3000.00 1000.00 1 0.13390736E+01 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 2 -0.56823331E+04-0.46719711E+01 0.13390736E+01 0.00000000E+00 0.00000000E+00 3 0.00000000E+00 0.00000000E+00-0.56823331E+04-0.46719711E+01 4 OH(s) H 1O 1PD 1 0 300.00 3000.00 1000.00 1 0.29667975E+01 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 2 -0.17280136E+05-0.57841845E+01 0.29667975E+01 0.00000000E+00 0.00000000E+00 3 0.00000000E+00 0.00000000E+00-0.17280136E+05-0.57841845E+01 4 CO(s) C 1O 1PD 1 0 300.00 3000.00 1000.00 1 0.33258191E+01 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 2 -0.30999945E+05-0.84931928E+01 0.33258191E+01 0.00000000E+00 0.00000000E+00 3 0.00000000E+00 0.00000000E+00-0.30999945E+05-0.84931928E+01 4 C(s) C 1PD 1 0 0 300.00 3000.00 1000.00 1 0.15708761E+01 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 2 0.61431172E+04-0.84757985E+01 0.15708761E+01 0.00000000E+00 0.00000000E+00 3 0.00000000E+00 0.00000000E+00 0.61431172E+04-0.84757985E+01 4 CH3(s) C 1H 3PD 1 0 300.00 3000.00 1000.00 1 0.52064396E+01 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 2 -0.59209000E+04-0.23526324E+02 0.52064396E+01 0.00000000E+00 0.00000000E+00 3 0.00000000E+00 0.00000000E+00-0.59209000E+04-0.23526324E+02 4 CH2(s) C 1H 2PD 1 0 300.00 3000.00 1000.00 1 0.39945851E+01 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 2 0.78325504E+04-0.12369255E+02 0.39945851E+01 0.00000000E+00 0.00000000E+00 3 0.00000000E+00 0.00000000E+00 0.78325504E+04-0.12369255E+02 4 CH(s) C 1H 1PD 1 0 300.00 3000.00 1000.00 1 0.27827306E+01 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 2 0.17911653E+05-0.10422527E+02 0.27827306E+01 0.00000000E+00 0.00000000E+00 3 0.00000000E+00 0.00000000E+00 0.17911653E+05-0.10422527E+02 4 CH4(s) C 1H 4PD 1 0 300.00 3000.00 1000.00 1 0.64182942E+01 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 2 -0.15037816E+05-0.30840663E+02 0.64182942E+01 0.00000000E+00 0.00000000E+00 3 0.00000000E+00 0.00000000E+00-0.15037816E+05-0.30840663E+02 4 O(s) O 1PD 1 0 0 300.00 3000.00 1000.00 1 0.17469827E+01 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 2 -0.13833477E+05-0.54508350E+01 0.17469827E+01 0.00000000E+00 0.00000000E+00 3 0.00000000E+00 0.00000000E+00-0.13833477E+05-0.54508350E+01 4 CO2(s) C 1O 2PD 1 0 300.00 3000.00 1000.00 1 0.51774369E+01 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 2 -0.52230997E+05-0.19695100E+02 0.51774369E+01 0.00000000E+00 0.00000000E+00 3 0.00000000E+00 0.00000000E+00-0.52230997E+05-0.19695100E+02 4 COOH(s) C 1H 1O 2PD 1 300.00 5000.00 1000.00 1 0.63281840E+01 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 2 -0.46032613E+05-0.18598657E+02 0.63281840E+01 0.00000000E+00 0.00000000E+00 3 0.00000000E+00 0.00000000E+00-0.46032613E+05-0.18598657E+02 4 H3CO(s) C 1H 3O 1PD 1 300.00 5000.00 1000.00 1 0.68824039E+01 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 2 -0.32413545E+05-0.27597954E+02 0.68824039E+01 0.00000000E+00 0.00000000E+00 3 0.00000000E+00 0.00000000E+00-0.32413545E+05-0.27597954E+02 4 H2CO(s) C 1H 2O 1PD 1 300.00 5000.00 1000.00 1 0.56968756E+01 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 2 -0.27905173E+05-0.21229700E+02 0.56968756E+01 0.00000000E+00 0.00000000E+00 3 0.00000000E+00 0.00000000E+00-0.27905173E+05-0.21229700E+02 4 HCO(s) C 1H 1O 1PD 1 300.00 5000.00 1000.00 1 0.45113474E+01 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 2 -0.22530833E+05-0.14861447E+02 0.45113474E+01 0.00000000E+00 0.00000000E+00 3 0.00000000E+00 0.00000000E+00-0.22530833E+05-0.14861447E+02 4 CH4 C 1H 4 0 0 300.00 5000.00 1000.00 1 0.16834788E+01 0.10237236E-01-0.38751286E-05 0.67855849E-09-0.45034231E-13 2 -0.10080787E+05 0.96233950E+01 0.77874148E+00 0.17476683E-01-0.27834090E-04 3 0.30497080E-07-0.12239307E-10-0.98252285E+04 0.13722195E+02 4 O2 O 2 0 0 0 300.00 5000.00 1000.00 1 0.36122139E+01 0.74853166E-03-0.19820647E-06 0.33749008E-10-0.23907374E-14 2 -0.11978151E+04 0.36703307E+01 0.37837135E+01-0.30233634E-02 0.99492751E-05 3 -0.98189101E-08 0.33031825E-11-0.10638107E+04 0.36416345E+01 4 CO C 1O 1 0 0 300.00 5000.00 1000.00 1 0.30250781E+01 0.14426885E-02-0.56308278E-06 0.10185813E-09-0.69109516E-14 2 -0.14268350E+05 0.61082177E+01 0.32624517E+01 0.15119409E-02-0.38817552E-05 3 0.55819442E-08-0.24749512E-11-0.14310539E+05 0.48488970E+01 4 CO2 C 1O 2 0 0 300.00 5000.00 1000.00 1 0.44536228E+01 0.31401687E-02-0.12784105E-05 0.23939967E-09-0.16690332E-13 2 -0.48966961E+05-0.95539588E+00 0.22757246E+01 0.99220723E-02-0.10409113E-04 3 0.68666868E-08-0.21172801E-11-0.48373141E+05 0.10188488E+02 4 H2 H 2 0 0 0 300.00 5000.00 1000.00 1 0.30667095E+01 0.57473755E-03 0.13938319E-07-0.25483518E-10 0.29098574E-14 2 -0.86547412E+03-0.17798424E+01 0.33553514E+01 0.50136144E-03-0.23006908E-06 3 -0.47905324E-09 0.48522585E-12-0.10191626E+04-0.35477228E+01 4 H2O H 2O 1 0 0 300.00 5000.00 1000.00 1 0.26110472E+01 0.31563130E-02-0.92985438E-06 0.13331538E-09-0.74689351E-14 2 -0.29868167E+05 0.72091268E+01 0.41677234E+01-0.18114970E-02 0.59471288E-05 3 -0.48692021E-08 0.15291991E-11-0.30289969E+05-0.73135474E+00 4 N2 N 2 0 0 0 300.00 5000.00 1000.00 1 0.28532899E+01 0.16022128E-02-0.62936893E-06 0.11441022E-09-0.78057465E-14 2 -0.89008093E+03 0.63964897E+01 0.37044177E+01-0.14218753E-02 0.28670392E-05 3 -0.12028885E-08-0.13954677E-13-0.10640795E+04 0.22336285E+01 4 ! REACTIONS KJOULES/MOLE MWOFF H2 + Pd(s) + Pd(s) => H(s) + H(s) 2.445E-01 -0.076 0.000 STICK O2 + Pd(s) + Pd(s) => 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 H2O + Pd(s) => H2O(s) 1.402E-01 0.033 0.000 STICK CO2 + Pd(s) => 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) => H3CO(s) + OH(s) 8.928E-03 0.004 159.978 STICK COV / O(s) 0.000E+00 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 COV / O(s) 0.000E+00 0.000 -22.500 / H2O(s) => Pd(s) + H2O 1.244E+14 -0.134 46.593 CO(s) => Pd(s) + CO 8.565E+13 -0.062 138.558 COV / CO(s) 0.000E+00 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 H3CO(s) + OH(s) => O(s) + O(s) + CH4 2.046E+18 -0.017 248.686 O(s) + H(s) => OH(s) + Pd(s) 3.598E+22 -0.060 85.044 COV / O(s) 0.000E+00 0.000 -11.250 / OH(s) + Pd(s) => O(s) + H(s) 4.169E+20 0.060 66.456 OH(s) + H(s) => H2O(s) + Pd(s) 3.017E+20 -0.059 -0.823 H2O(s) + Pd(s) => OH(s) + H(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 COV / O(s) 0.000E+00 0.000 -11.250 / O(s) + C(s) => CO(s) + Pd(s) 5.434E+23 0.004 21.097 COV / O(s) 0.000E+00 0.000 -11.250 / CO(s) + Pd(s) => O(s) + C(s) 2.392E+21 -0.004 214.903 COV / CO(s) 0.000E+00 0.000 -31.000 / O(s) + CO(s) => CO2(s) + Pd(s) 6.874E+18 0.052 71.247 COV / O(s) 0.000E+00 0.000 -11.250 / COV / CO(s) 0.000E+00 0.000 -31.000 / CO2(s) + Pd(s) => O(s) + CO(s) 2.400E+21 -0.052 132.753 CH4(s) + Pd(s) => CH3(s) + H(s) 1.301E+22 0.064 66.978 CH3(s) + H(s) => CH4(s) + Pd(s) 1.052E+21 -0.064 38.422 CH3(s) + Pd(s) => CH2(s) + H(s) 2.811E+24 0.064 104.253 CH2(s) + H(s) => CH3(s) + Pd(s) 4.871E+21 -0.064 37.147 CH2(s) + Pd(s) => CH(s) + H(s) 8.888E+23 0.064 100.278 CH(s) + H(s) => CH2(s) + Pd(s) 1.540E+25 -0.064 63.722 CH(s) + Pd(s) => C(s) + H(s) 2.811E+23 0.064 20.753 C(s) + H(s) => CH(s) + Pd(s) 4.871E+24 -0.064 165.847 O(s) + CH4(s) => CH3(s) + OH(s) 2.591E+24 0.004 96.622 COV / O(s) 0.000E+00 0.000 -11.250 / CH3(s) + OH(s) => O(s) + CH4(s) 2.427E+21 -0.004 49.478 O(s) + CH3(s) => CH2(s) + OH(s) 2.611E+25 0.004 97.347 COV / O(s) 0.000E+00 0.000 -11.250 / CH2(s) + OH(s) => O(s) + CH3(s) 5.243E+20 -0.004 11.653 O(s) + CH2(s) => CH(s) + OH(s) 8.257E+21 0.004 88.322 COV / O(s) 0.000E+00 0.000 -11.250 / CH(s) + OH(s) => O(s) + CH2(s) 1.658E+21 -0.004 33.178 O(s) + CH(s) => C(s) + OH(s) 2.611E+21 0.004 36.847 COV / O(s) 0.000E+00 0.000 -11.250 / C(s) + OH(s) => O(s) + CH(s) 5.243E+20 -0.004 163.353 C(s) + OH(s) => CO(s) + H(s) 1.898E+22 0.064 0.503 CO(s) + H(s) => C(s) + OH(s) 7.213E+21 -0.064 212.897 COV / CO(s) 0.000E+00 0.000 -31.000 / H3CO(s) + O(s) => H2CO(s) + OH(s) 2.351E+24 0.017 65.714 COV / O(s) 0.000E+00 0.000 -11.250 / H2CO(s) + OH(s) => H3CO(s) + O(s) 5.824E+21 -0.017 56.886 H2CO(s) + O(s) => HCO(s) + OH(s) 2.351E+24 0.017 31.014 COV / O(s) 0.000E+00 0.000 -11.250 / HCO(s) + OH(s) => H2CO(s) + O(s) 5.824E+21 -0.017 14.986 HCO(s) + O(s) => CO(s) + OH(s) 2.351E+24 0.017 12.114 COV / O(s) 0.000E+00 0.000 -11.250 / CO(s) + OH(s) => HCO(s) + O(s) 5.824E+21 -0.017 111.186 COV / CO(s) 0.000E+00 0.000 -31.000 / CO(s) + OH(s) => COOH(s) + Pd(s) 4.167E+19 0.018 46.493 COV / CO(s) 0.000E+00 0.000 -31.000 / COOH(s) + Pd(s) => CO(s) + OH(s) 3.251E+21 -0.018 27.807 COOH(s) + Pd(s) => CO2(s) + H(s) 1.871E+19 0.094 27.009 CO2(s) + H(s) => COOH(s) + Pd(s) 7.228E+21 -0.094 125.791 COOH(s) + H(s) => CO(s) + H2O(s) 2.532E+18 -0.076 61.084 CO(s) + H2O(s) => COOH(s) + H(s) 5.349E+18 0.076 190.216 COV / CO(s) 0.000E+00 0.000 -31.000 / END