!----------------------------------------------------------------------! !SURFACE MECHANISM OF THE PARTIAL OXIDATION OF CH4 ON RHODIUM !*********************************************************************** !**** * !**** CPO OF CH4 ON Rh - SURFACE MECHANISM * !**** * !**** Version 1.1 March, 2003 * !**** * !**** R. Schwiedernoch, L. Maier, O. Deutschmann, * !**** Karlsruhe University, Germany * !**** * !**** * !**** Ref: R. Schwiedernoch, S. Tischer, C. Correa, O. Deutschmann.* !**** Experimental and Numerical Study of the Transient Behavior of * !**** a Catalytic Partial Oxidation Monolith, Chem. Eng. Sci. 58 * !**** (2003), 633-642 * !**** * !**** * !**** 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(s) H2O(s) H(s) OH(s) CO(s) C(s) CH3(s) CH2(s) CH(s) CH4(s) O(s) CO2(s) END ! THERMO ALL 300.0 1000.0 3000.0 ! all data are dummy data (they are not needed - all rxns irrev.) O(s) 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(s) 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(s) 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(s) 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(s) 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(s) 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(s) 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(s) 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(s) 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(s) 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(s) 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(s) 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(s) +Rh(s) =>H(s) +H(s) 0.010E-00 0.0 0.0 STICK O2 +Rh(s) +Rh(s) =>O(s) +O(s) 0.010E-00 0.0 0.0 STICK CH4 +Rh(s) =>CH4(s) 8.000E-03 0.0 0.0 STICK H2O +Rh(s) =>H2O(s) 1.000E-01 0.0 0.0 STICK CO2 +Rh(s) =>CO2(s) 1.000E-05 0.0 0.0 STICK CO +Rh(s) =>CO(s) 5.000E-01 0.0 0.0 STICK !*********************************************************************** !**** 2. DESORPTION !*********************************************************************** H(s) +H(s) =>Rh(s) +Rh(s) +H2 3.000E+21 0.0 77800 O(s) +O(s) =>Rh(s) +Rh(s) +O2 1.300E+22 0.0 355200 COV / O(s) 0. 0. -280000. / H2O(s) =>H2O +Rh(s) 3.000E+13 0.0 45000 CO(s) =>CO +Rh(s) 3.500E+13 0.0 133400 COV / CO(s) 0. 0. -15000. / CO2(s) =>CO2 +Rh(s) 1.000E+13 0.0 21700 CH4(s) =>CH4 +Rh(s) 1.000E+13 0.0 25100 !*********************************************************************** !**** 3. SURFACE REACTIONS !*********************************************************************** H(s) +O(s) =>OH(s) +Rh(s) 5.000E+22 0.0 83700 OH(s) +Rh(s) =>H(s) +O(s) 3.000E+20 0.0 37700 H(s) +OH(s) =>H2O(s) +Rh(s) 3.000E+20 0.0 33500 H2O(s) +Rh(s) =>H(s) +OH(s) 5.000E+22 0.0 104700 OH(s) +OH(s) =>H2O(s) +O(s) 3.000E+21 0.0 100800 H2O(s) +O(s) =>OH(s) +OH(s) 3.000E+21 0.0 171800 C(s) +O(s) =>CO(s) +Rh(s) 3.000E+22 0.0 97900 CO(s) +Rh(s) =>C(s) +O(s) 2.500E+21 0.0 169000 CO(s) +O(s) =>CO2(s) +Rh(s) 1.400E+20 0.0 121600 CO2(s) +Rh(s) =>CO(s) +O(s) 3.000E+21 0.0 115300 !*********************************************************************** CH4(s) +Rh(s) =>CH3(s) +H(s) 3.700E+21 0.0 61000 CH3(s) +H(s) =>CH4(s) +Rh(s) 3.700E+21 0.0 51000 CH3(s) +Rh(s) =>CH2(s) +H(s) 3.700E+24 0.0 103000 CH2(s) +H(s) =>CH3(s) +Rh(s) 3.700E+21 0.0 44000 CH2(s) +Rh(s) =>CH(s) +H(s) 3.700E+24 0.0 100000 CH(s) +H(s) =>CH2(s) +Rh(s) 3.700E+21 0.0 68000 CH(s) +Rh(s) =>C(s) +H(s) 3.700E+21 0.0 21000 C(s) +H(s) =>CH(s) +Rh(s) 3.700E+21 0.0 172800 !*********************************************************************** CH4(s) +O(s) =>CH3(s) +OH(s) 1.700E+24 0.0 80300 CH3(s) +OH(s) =>CH4(s) +O(s) 3.700E+21 0.0 24300 CH3(s) +O(s) =>CH2(s) +OH(s) 3.700E+24 0.0 120300 CH2(s) +OH(s) =>CH3(s) +O(s) 3.700E+21 0.0 15100 CH2(s) +O(s) =>CH(s) +OH(s) 3.700E+24 0.0 158400 CH(s) +OH(s) =>CH2(s) +O(s) 3.700E+21 0.0 36800 CH(s) +O(s) =>C(s) +OH(s) 3.700E+21 0.0 30100 C(s) +OH(s) =>CH(s) +O(s) 3.700E+21 0.0 145500 !*********************************************************************** END