!SURFACE MECHANISM OF CH4 REFORMING AND OXIDATION OVER NI !*********************************************************************** !**** * !**** CH4 ON Ni - SURFACE MECHANISM * !**** * !**** Version 1.0 January 21, 2005 * !**** * !**** L. Maier, O. Deutschmann * !**** University of Karlsruhe, Germany * !**** Contact: mail@detchem.com (O. Deutschmann) * !**** * !**** * !**** NOTE: That is a first version that needs further * !**** improvements, * !**** e.g. NiO formation, coking, * !**** temp. range around 800C now * !**** * !**** * !**** Ref: E. Hecht, G.K. Gupta, H. Zhu. A.M. Dean, R.J. Kee, * !**** L. Maier, O. Deutschmann. * !**** Applied Catalysis A: General 295 (2005) 40–51 * !**** * !**** Kinetic data format: DETCHEM * !**** k = A * T**b * exp (-Ea/RT) A b Ea * !**** (cm,mol,s) - kJ/mol * !**** * !**** STICK: A in next reaction is initial sticking coefficient * !**** * !**** $.. : additional coverage dependence of Ea (3rd column) * !**** or changed reaction order (2nd column) * !**** * !**** see manuals on www.detchem.com for details * !**** * !**** The kinetic data of the backward reactions are calculated * !**** from thermodynamics (k_b = k_f /K) at 800 C * !**** * !**** Surface site density: 2.60E-9 mol/cm**2 * !**** * !**** CHEMKIN format * !**** * !*********************************************************************** REACTIONS KJOULES/MOLE MWOFF H2 + _Ni_ + _Ni_ => H_Ni + H_Ni 1.000E-02 0.000 0.000 STICK H_Ni + H_Ni => _Ni_ + _Ni_ + H2 5.593E+19 0.000 88.120 O2 + _Ni_ + _Ni_ => O_Ni + O_Ni 1.000E-02 0.000 0.000 STICK O_Ni + O_Ni => _Ni_ + _Ni_ + O2 2.508E+23 0.000 470.390 CH4 + _Ni_ => CH4_Ni 8.000E-03 0.000 0.000 STICK CH4_Ni => _Ni_ + CH4 5.302E+15 0.000 33.150 H2O + _Ni_ => H2O_Ni 1.000E-01 0.000 0.000 STICK H2O_Ni => _Ni_ + H2O 4.579E+12 0.000 62.680 CO2 + _Ni_ => CO2_Ni 1.000E-05 0.000 0.000 STICK CO2_Ni => _Ni_ + CO2 9.334E+07 0.000 28.800 CO + _Ni_ => CO_Ni 5.000E-01 0.000 0.000 STICK CO_Ni => _Ni_ + CO 4.041E+11 0.000 112.850 COV / CO_Ni 0.000E+00 0.000 -50.000 / O_Ni + H_Ni => OH_Ni + _Ni_ 5.000E+22 0.000 97.900 OH_Ni + _Ni_ => O_Ni + H_Ni 2.005E+21 0.000 37.190 OH_Ni + H_Ni => _Ni_ + H2O_Ni 3.000E+20 0.000 42.700 _Ni_ + H2O_Ni => OH_Ni + H_Ni 2.175E+21 0.000 91.360 OH_Ni + OH_Ni => O_Ni + H2O_Ni 3.000E+21 0.000 100.000 O_Ni + H2O_Ni => OH_Ni + OH_Ni 5.423E+23 0.000 209.370 O_Ni + C_Ni => _Ni_ + CO_Ni 5.200E+23 0.000 148.100 _Ni_ + CO_Ni => O_Ni + C_Ni 1.418E+22 -3.000 115.970 COV / CO_Ni 0.000E+00 0.000 -50.000 / O_Ni + CO_Ni => _Ni_ + CO2_Ni 2.000E+19 0.000 123.600 COV / CO_Ni 0.000E+00 0.000 -50.000 / _Ni_ + CO2_Ni => O_Ni + CO_Ni 3.214E+23 -1.000 86.500 _Ni_ + HCO_Ni => H_Ni + CO_Ni 3.700E+21 0.000 0.000 COV / CO_Ni 0.000E+00 0.000 50.000 / H_Ni + CO_Ni => _Ni_ + HCO_Ni 2.338E+20 -1.000 127.980 _Ni_ + HCO_Ni => O_Ni + CH_Ni 3.700E+24 -3.000 95.800 O_Ni + CH_Ni => _Ni_ + HCO_Ni 7.914E+20 0.000 114.220 _Ni_ + CH4_Ni => H_Ni + CH3_Ni 3.700E+21 0.000 57.700 H_Ni + CH3_Ni => _Ni_ + CH4_Ni 4.438E+21 0.000 58.830 _Ni_ + CH3_Ni => H_Ni + CH2_Ni 3.700E+24 0.000 100.000 H_Ni + CH2_Ni => _Ni_ + CH3_Ni 9.513E+22 0.000 52.580 _Ni_ + CH2_Ni => H_Ni + CH_Ni 3.700E+24 0.000 97.100 H_Ni + CH_Ni => _Ni_ + CH2_Ni 3.008E+24 0.000 76.430 _Ni_ + CH_Ni => H_Ni + C_Ni 3.700E+21 0.000 18.800 H_Ni + C_Ni => _Ni_ + CH_Ni 4.400E+22 0.000 160.490 O_Ni + CH4_Ni => OH_Ni + CH3_Ni 1.700E+24 0.000 88.300 OH_Ni + CH3_Ni => O_Ni + CH4_Ni 8.178E+22 0.000 28.720 O_Ni + CH3_Ni => OH_Ni + CH2_Ni 3.700E+24 0.000 130.100 OH_Ni + CH2_Ni => O_Ni + CH3_Ni 3.815E+21 0.000 21.970 O_Ni + CH2_Ni => OH_Ni + CH_Ni 3.700E+24 0.000 126.800 OH_Ni + CH_Ni => O_Ni + CH2_Ni 1.206E+23 0.000 45.420 O_Ni + CH_Ni => OH_Ni + C_Ni 3.700E+21 0.000 48.100 OH_Ni + C_Ni => O_Ni + CH_Ni 1.764E+21 0.000 129.080 END