!-------------------------------------------------------------------------! !SURFACE MECHANISM OF THE PARTIAL OXIDATION OF CH4 ON RHODIUM !*********************************************************************** !**** * !**** CPO OF CH4 ON Rh - SURFACE MECHANISM * !**** * !**** Version 1.0 February 13, 2001 * !**** * !**** O. Deutschmann, R. Schwiedernoch, L. Maier, * !**** Heidelberg University, Germany * !**** * !**** * !**** NOTE: That is a first version that needs further * !**** improvements, e.g. methanization, reforming etc.!!! * !**** * !**** * !**** Ref: O. Deutschmann, R. Schwiedernoch, L.I. Maier, * !**** D. Chatterjee. Natural Gas Conversion in Monolithic * !**** Catalysts: Interaction of Chemical Reactions and * !**** Transport Phenomena. Natural Gas Conversion VI, * !**** Studies in Surface Science and Catalysis 136, * !**** E. Iglesia, J.J. Spivey, T.H. Fleisch (eds.), * !**** p. 215-258, Elsevier, 2001 * !**** * !**** Kinetic data: * !**** k = A * T**b * exp (-Ea/RT) A b Ea * !**** (cm,mol,s) - J/mol * !**** * !**** * !**** SURFACE CHEMKIN format 21.01.06, tested with Vers.4.0.1 * !**** * !*********************************************************************** SITE/RH_SURFACE/ SDEN/2.72E-9/ _Rh_ H2O_Rh H_Rh OH_Rh CO_Rh C_Rh CH3_Rh CH2_Rh CH_Rh CH4_Rh O_Rh CO2_Rh END ! THERMO ALL 300.0 1000.0 3000.0 ! all data are dummy data (they are not needed - all rxns irrev.) O_Rh O 1Rh 1 I 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 O2(s) O 2Rh 1 I 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 H_Rh H 1Rh 1 I 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 H2(s) H 2Rh 1 I 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_Rh O 1H 2Rh 1 I 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 OH_Rh O 1H 1Rh 1 I 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 _Rh_ Rh 1 S 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 CO_Rh C 1O 1Rh 1 I 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 CO2_Rh C 1O 2Rh 1 I 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 C_Rh C 1Rh 1 I 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 CH_Rh C 1H 1Rh 1 I 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 CH2_Rh C 1H 2Rh 1 I 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 CH3_Rh C 1H 3Rh 1 I 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 CH4_Rh C 1H 4Rh 1 I 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 END ! REACTIONS JOULES/MOLE !*********************************************************************** !**** 1. ADSORPTION !*********************************************************************** H2 +_Rh_ +_Rh_ =>H_Rh +H_Rh 0.010E-00 0.0 0.0 STICK O2 +_Rh_ +_Rh_ =>O_Rh +O_Rh 0.010E-00 0.0 0.0 STICK CH4 +_Rh_ =>CH4_Rh 8.000E-03 0.0 0.0 STICK H2O +_Rh_ =>H2O_Rh 1.000E-01 0.0 0.0 STICK CO2 +_Rh_ =>CO2_Rh 1.000E-05 0.0 0.0 STICK CO +_Rh_ =>CO_Rh 5.000E-01 0.0 0.0 STICK !*********************************************************************** !**** 2. DESORPTION !*********************************************************************** H_Rh +H_Rh =>_Rh_ +_Rh_ +H2 3.000E+21 0.0 77800 O_Rh +O_Rh =>_Rh_ +_Rh_ +O2 1.300E+22 0.0 355200 H2O_Rh =>H2O +_Rh_ 3.000E+13 0.0 45000 CO_Rh =>CO +_Rh_ 3.500E+13 0.0 133400 CO2_Rh =>CO2 +_Rh_ 1.000E+13 0.0 21700 CH4_Rh =>CH4 +_Rh_ 1.000E+13 0.0 25100 !*********************************************************************** !**** 3. SURFACE REACTIONS !*********************************************************************** H_Rh +O_Rh =>OH_Rh +_Rh_ 5.000E+22 0.0 83700 OH_Rh +_Rh_ =>H_Rh +O_Rh 3.000E+20 0.0 37700 H_Rh +OH_Rh =>H2O_Rh +_Rh_ 3.000E+20 0.0 33500 H2O_Rh +_Rh_ =>H_Rh +OH_Rh 5.000E+22 0.0 106400 OH_Rh +OH_Rh =>H2O_Rh +O_Rh 3.000E+21 0.0 100800 H2O_Rh +O_Rh =>OH_Rh +OH_Rh 3.000E+21 0.0 224200 C_Rh +O_Rh =>CO_Rh +_Rh_ 3.000E+22 0.0 97900 CO_Rh +_Rh_ =>C_Rh +O_Rh 2.500E+21 0.0 169000 CO_Rh +O_Rh =>CO2_Rh +_Rh_ 1.400E+20 0.0 121600 CO2_Rh +_Rh_ =>CO_Rh +O_Rh 3.000E+21 0.0 115300 !*********************************************************************** CH4_Rh +_Rh_ =>CH3_Rh +H_Rh 3.700E+21 0.0 61000 CH3_Rh +H_Rh =>CH4_Rh +_Rh_ 3.700E+21 0.0 51000 CH3_Rh +_Rh_ =>CH2_Rh +H_Rh 3.700E+24 0.0 103000 CH2_Rh +H_Rh =>CH3_Rh +_Rh_ 3.700E+21 0.0 44000 CH2_Rh +_Rh_ =>CH_Rh +H_Rh 3.700E+24 0.0 100000 CH_Rh +H_Rh =>CH2_Rh +_Rh_ 3.700E+21 0.0 68000 CH_Rh +_Rh_ =>C_Rh +H_Rh 3.700E+21 0.0 21000 C_Rh +H_Rh =>CH_Rh +_Rh_ 3.700E+21 0.0 172800 !*********************************************************************** CH4_Rh +O_Rh =>CH3_Rh +OH_Rh 1.700E+24 0.0 80300 CH3_Rh +OH_Rh =>CH4_Rh +O_Rh 3.700E+21 0.0 24300 CH3_Rh +O_Rh =>CH2_Rh +OH_Rh 3.700E+24 0.0 120300 CH2_Rh +OH_Rh =>CH3_Rh +O_Rh 3.700E+21 0.0 15100 CH2_Rh +O_Rh =>CH_Rh +OH_Rh 3.700E+24 0.0 158400 CH_Rh +OH_Rh =>CH2_Rh +O_Rh 3.700E+21 0.0 36800 CH_Rh +O_Rh =>C_Rh +OH_Rh 3.700E+21 0.0 30100 C_Rh +OH_Rh =>CH_Rh +O_Rh 3.700E+21 0.0 145500 !*********************************************************************** END