!SURFACE MECHANISM FOR STEAM REFORMING AND PARTIAL OXIDATION OF METHANE !OVER RHODIUM !*********************************************************************** !**** * !**** SR/CPO CH4 ON RH - SURFACE MECHANISM * !**** * !**** Version 2.0, March 2008 * !**** L. Maier, O. Deutschmann * !**** KIT (Karlsruhe Institute of Technology) * !**** Contact: mail@detchem.com (O. Deutschmann) * !**** * !**** References: * !**** J. Thormann, L. Maier, P. Pfeifer, U. Kunz, K. Schubert, * !**** O. Deutschmann.International J. Hydrogen Energy * !**** 34 (2009), 5108-5120 * !**** 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 * !**** * !**** * !**** (SURFACE CHEMKIN format) * !**** * !*********************************************************************** 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) HCO(s) END THERMO ALL CH4 C 1H 4 0 0 300.00 5000.00 1000.00 0.16834780E+01 0.10237236E-01-0.38751280E-05 0.67855850E-09-0.45034230E-13 -0.10080787E+05 0.96233950E+01 0.77874150E+00 0.17476680E-01-0.27834090E-04 0.30497080E-07-0.12239307E-10-0.98252290E+04 0.13722195E+02 O2 O 2 0 0 0 300.00 5000.00 1000.00 0.36975780E+01 0.61351970E-03-0.12588420E-06 0.17752810E-10-0.11364354E-14 -0.12339301E+04 0.31891650E+01 0.32129360E+01 0.11274864E-02-0.57561500E-06 0.13138773E-08-0.87685540E-12-0.10052490E+04 0.60347370E+01 CO C 1O 1 0 0 300.00 5000.00 1000.00 0.30250780E+01 0.14426885E-02-0.56308270E-06 0.10185813E-09-0.69109510E-14 -0.14268350E+05 0.61082170E+01 0.32624510E+01 0.15119409E-02-0.38817550E-05 0.55819440E-08-0.24749510E-11-0.14310539E+05 0.48488970E+01 CO2 C 1O 2 0 0 300.00 5000.00 1000.00 0.44536230E+01 0.31401680E-02-0.12784105E-05 0.23939960E-09-0.16690333E-13 -0.48966960E+05-0.95539590E+00 0.22757240E+01 0.99220720E-02-0.10409113E-04 0.68666860E-08-0.21172800E-11-0.48373140E+05 0.10188488E+02 H2 H 2 0 0 0 300.00 5000.00 1000.00 0.29914230E+01 0.70006440E-03-0.56338280E-07-0.92315780E-11 0.15827519E-14 -0.83503400E+03-0.13551101E+01 0.32981240E+01 0.82494410E-03-0.81430150E-06 -0.94754340E-10 0.41348720E-12-0.10125209E+04-0.32940940E+01 H2O H 2O 1 0 0 300.00 5000.00 1000.00 0.26721450E+01 0.30562930E-02-0.87302600E-06 0.12009964E-09-0.63916180E-14 -0.29899210E+05 0.68628170E+01 0.33868420E+01 0.34749820E-02-0.63546960E-05 0.69685810E-08-0.25065880E-11-0.30208110E+05 0.25902320E+01 N2 N 2 0 0 0 300.00 5000.00 1000.00 0.29266400E+01 0.14879768E-02-0.56847600E-06 0.10097038E-09-0.67533510E-14 -0.92279770E+03 0.59805280E+01 0.32986770E+01 0.14082404E-02-0.39632220E-05 0.56415150E-08-0.24448540E-11-0.10208999E+04 0.39503720E+01 RH(s) RH 1 0 0 0 300.00 3000.00 1000.00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 H2O(s) H 2O 1RH 1 0 293.00 5000.00 5000.00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 -0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00-0.00000000E+00 0.00000000E+00 H(s) H 1RH 1 0 0 293.00 5000.00 5000.00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 -0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00-0.00000000E+00 0.00000000E+00 OH(s) H 1O 1RH 1 0 293.00 5000.00 5000.00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 -0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 CO(s) C 1O 1RH 1 0 293.00 5000.00 5000.00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 -0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00-0.00000000E+00 0.00000000E+00 C(s) C 1RH 1 0 0 293.00 5000.00 5000.00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 -0.00000000E+00-0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00-0.00000000E+00-0.00000000E+00 CH3(s) C 1H 3RH 1 0 300.00 450.00 450.00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 -0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00-0.00000000E+00 0.00000000E+00 CH2(s) C 1H 2RH 1 0 300.00 450.00 450.00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 -0.00000000E+00-0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00-0.00000000E+00-0.00000000E+00 CH(s) C 1H 1RH 1 0 293.00 5000.00 5000.00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00-0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00-0.00000000E+00 CH4(s) C 1H 4RH 1 0 293.00 5000.00 5000.00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 -0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00-0.00000000E+00 0.00000000E+00 O(s) O 1RH 1 0 0 293.00 5000.00 5000.00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 -0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00-0.00000000E+00 0.00000000E+00 CO2(s) C 1O 2RH 1 0 293.00 5000.00 5000.00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 -0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00-0.00000000E+00 0.00000000E+00 HCO(s) C 1H 1O 2RH 1 300.00 450.00 450.00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 -0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00-0.00000000E+00 0.00000000E+00 END REACTIONS JOULES/MOLE MWOFF H2 + RH(s) + RH(s) => H(s) + H(s) 0.01 0. 0. STICK H(s) + H(s) => RH(s) + RH(s) + H2 3.E+21 0. 77800. O2 + RH(s) + RH(s) => O(s) + O(s) 0.01 0. 0. STICK O(s) + O(s) => RH(s) + RH(s) + O2 1.3E+22 0. 355200. CH4 + RH(s) => CH4(s) 0.008 0. 0. STICK CH4(s) => RH(s) + CH4 2.E+14 0. 25100. H2O + RH(s) => H2O(s) 0.1 0. 0. STICK H2O(s) => RH(s) + H2O 6.E+13 0. 45000. CO2 + RH(s) => CO2(s) 0.00001 0. 0. STICK CO2(s) => RH(s) + CO2 3.E+8 0. 21700. CO + RH(s) => CO(s) 0.5 0. 0. STICK CO(s) => RH(s) + CO 1.E+13 0. 133400. COV / CO(s) 0. 0. -50000. / O(s) + H(s) => OH(s) + RH(s) 5.E+22 0. 83700. OH(s) + RH(s) => O(s) + H(s) 3.E+20 0. 37700. OH(s) + H(s) => H2O(s) + RH(s) 3.E+20 0. 33500. H2O(s) + RH(s) => OH(s) + H(s) 5.E+22 0. 106400. OH(s) + OH(s) => O(s) + H2O(s) 3.E+21 0. 100800. O(s) + H2O(s) => OH(s) + OH(s) 3.E+21 0. 171800. O(s) + C(s) => CO(s) + RH(s) 5.E+23 0. 97900. CO(s) + RH(s) => O(s) + C(s) 3.7E+21 0. 169000. COV / CO(s) 0. 0. -50000. / O(s) + CO(s) => CO2(s) + RH(s) 1.E+19 0. 121600. COV / CO(s) 0. 0. -50000. / CO2(s) + RH(s) => O(s) + CO(s) 5.E+21 0. 115300. CO(s) + H(s) => HCO(s) + RH(s) 5.E+19 0. 108900. HCO(s) + RH(s) => CO(s) + H(s) 3.7E+21 0. 0. COV / CO(s) 0. 0. 50000. / HCO(s) + RH(s) => O(s) + CH(s) 8.E+23 0. 59500. O(s) + CH(s) => HCO(s) + RH(s) 3.7E+21 0. 167500. CH4(s) + RH(s) => CH3(s) + H(s) 5.5E+20 0. 61000. CH3(s) + H(s) => CH4(s) + RH(s) 3.7E+21 0. 51000. CH3(s) + RH(s) => CH2(s) + H(s) 3.7E+24 0. 103000. CH2(s) + H(s) => CH3(s) + RH(s) 3.7E+21 0. 44000. CH2(s) + RH(s) => CH(s) + H(s) 3.7E+24 0. 100000. CH(s) + H(s) => CH2(s) + RH(s) 3.7E+24 0. 68000. CH(s) + RH(s) => C(s) + H(s) 3.7E+21 0. 21000. C(s) + H(s) => CH(s) + RH(s) 3.7E+21 0. 172800. O(s) + CH4(s) => CH3(s) + OH(s) 1.7E+24 0. 80340. CH3(s) + OH(s) => O(s) + CH4(s) 3.7E+21 0. 24270. O(s) + CH3(s) => CH2(s) + OH(s) 3.7E+24 0. 120310. CH2(s) + OH(s) => O(s) + CH3(s) 3.7E+21 0. 15060. O(s) + CH2(s) => CH(s) + OH(s) 3.7E+24 0. 114500. CH(s) + OH(s) => O(s) + CH2(s) 3.7E+21 0. 36820. O(s) + CH(s) => C(s) + OH(s) 3.7E+21 0. 30130. C(s) + OH(s) => O(s) + CH(s) 3.7E+21 0. 136000. CO(s) + H(s) => C(s) + OH(s) 3.7E+21 0. 142760. C(s) + OH(s) => CO(s) + H(s) 3.7E+20 0. 25540. END