!SURFACE MECHANISM OF WATER-GAS SHIFT REACTION OVER RHODIUM !*********************************************************************** !**** * !**** H2/CO/O2/CO2/H2O OVER RH - SURFASE MECHANISM * !**** thermodynamically constant (273 - 1273K) * !**** * !**** References: * !**** C. Karakaya, R. Otterstätter, L. Maier, O. Deutschmann, * !**** Applied Catalysis A: General, submitted (2013) * !**** 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/Rh_surface/ SDEN/2.72E-9/ Rh(s) H2O(s) H(s) OH(s) CO(s) O(s) CO2(s) COOH(s) END THERMO 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 HCO(s) C 1H 1Rh 1O 1I 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 (adjust) C 1H 4 0 0 300.00 5000.00 1000.00 1 1.68347883E+00 1.02372356E-02-3.87512864E-06 6.78558487E-10-4.50342312E-14 2 -1.00807871E+04 9.62339497E+00 7.78741479E-01 1.74766835E-02-2.78340904E-05 3 3.04970804E-08-1.22393068E-11-9.82522852E+03 1.37221947E+01 4 O2 (adjust) O 2 0 0 0 300.00 5000.00 1000.00 1 3.61221390E+00 7.48531660E-04-1.98206470E-07 3.37490080E-11-2.39073740E-15 2 -1.19781510E+03 3.67033070E+00 3.78371350E+00-3.02336340E-03 9.94927510E-06 3 -9.81891010E-09 3.30318250E-12-1.06381070E+03 3.64163450E+00 4 CO (adjust) C 1O 1 0 0 300.00 5000.00 1000.00 1 3.02507806E+00 1.44268852E-03-5.63082779E-07 1.01858133E-10-6.91095156E-15 2 -1.42683496E+04 6.10821772E+00 3.26245165E+00 1.51194085E-03-3.88175522E-06 3 5.58194424E-09-2.47495123E-12-1.43105391E+04 4.84889698E+00 4 CO2 (adjust) C 1O 2 0 0 300.00 5000.00 1000.00 1 4.45362282E+00 3.14016873E-03-1.27841054E-06 2.39399667E-10-1.66903319E-14 2 -4.89669609E+04-9.55395877E-01 2.27572465E+00 9.92207229E-03-1.04091132E-05 3 6.86668678E-09-2.11728009E-12-4.83731406E+04 1.01884880E+01 4 H2 (adjust) H 2 0 0 0 300.00 5000.00 1000.00 1 3.06670950E+00 5.74737550E-04 1.39383190E-08-2.54835180E-11 2.90985740E-15 2 -8.65474120E+02-1.77984240E+00 3.35535140E+00 5.01361440E-04-2.30069080E-07 3 -4.79053240E-10 4.85225850E-13-1.01916260E+03-3.54772280E+00 4 H2O (adjust) H 2O 1 0 0 300.00 5000.00 1000.00 1 2.61104720E+00 3.15631300E-03-9.29854380E-07 1.33315380E-10-7.46893510E-15 2 -2.98681670E+04 7.20912680E+00 4.16772340E+00-1.81149700E-03 5.94712880E-06 3 -4.86920210E-09 1.52919910E-12-3.02899690E+04-7.31354740E-01 4 AR (adjust) AR 1 0 0 0 300.00 5000.00 1000.00 1 2.50000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 2 -7.45375020E+02 4.36600060E+00 2.50000000E+00 0.00000000E+00 0.00000000E+00 3 0.00000000E+00 0.00000000E+00-7.45374980E+02 4.36600060E+00 4 NI(*) (adjust) NI 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(*) (adjust) H 2O 1NI 1 0 293.00 5000.00 5000.00 1 1.00000000E-99 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 2 -3.28621348E+04 1.57219174E+01 1.00000000E-99 0.00000000E+00 0.00000000E+00 3 0.00000000E+00 0.00000000E+00-3.28621348E+04 1.57219174E+01 4 H(*) (adjust) H 1NI 1 0 0 293.00 5000.00 5000.00 1 1.00000000E-99 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 2 -3.82656399E+03 4.89898398E+00 1.00000000E-99 0.00000000E+00 0.00000000E+00 3 0.00000000E+00 0.00000000E+00-3.82656399E+03 4.89898398E+00 4 COOH(*) (adjust) C 1H 1O 2NI 1 300.00 5000.00 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(*) (adjust) H 1O 1NI 1 0 293.00 5000.00 5000.00 1 1.00000000E-99 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 2 -2.31833113E+04 1.28038592E+01 1.00000000E-99 0.00000000E+00 0.00000000E+00 3 0.00000000E+00 0.00000000E+00-2.31833113E+04 1.28038592E+01 4 CO(*) (adjust) C 1O 1NI 1 0 293.00 5000.00 5000.00 1 1.00000000E-99 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 2 -2.37539453E+04 1.96355620E+01 1.00000000E-99 0.00000000E+00 0.00000000E+00 3 0.00000000E+00 0.00000000E+00-2.37539453E+04 1.96355620E+01 4 C(*) (adjust) C 1NI 1 0 0 293.00 5000.00 5000.00 1 1.00000000E-99 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 2 -9.60170600E+02-9.94267012E+00 1.00000000E-99 0.00000000E+00 0.00000000E+00 3 0.00000000E+00 0.00000000E+00-9.60170600E+02-9.94267012E+00 4 CH3(*) (adjust) C 1H 3NI 1 0 293.00 5000.00 5000.00 1 1.00000000E-99 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 2 -3.58843376E+03 3.36230167E+00 1.00000000E-99 0.00000000E+00 0.00000000E+00 3 0.00000000E+00 0.00000000E+00-3.58843376E+03 3.36230167E+00 4 CH2(*) (adjust) C 1H 2NI 1 0 293.00 5000.00 5000.00 1 1.00000000E-99 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 2 5.94161025E+03 2.12413716E+00 1.00000000E-99 0.00000000E+00 0.00000000E+00 3 0.00000000E+00 0.00000000E+00 5.94161025E+03 2.12413716E+00 4 CH(*) (adjust) C 1H 1NI 1 0 293.00 5000.00 5000.00 1 1.00000000E-99 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 2 1.22543876E+04-2.56790500E+00 1.00000000E-99 0.00000000E+00 0.00000000E+00 3 0.00000000E+00 0.00000000E+00 1.22543876E+04-2.56790500E+00 4 CH4(*) (adjust) C 1H 4NI 1 0 293.00 5000.00 5000.00 1 1.00000000E-99 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 2 -7.27928907E+03 8.44319611E+00 1.00000000E-99 0.00000000E+00 0.00000000E+00 3 0.00000000E+00 0.00000000E+00-7.27928907E+03 8.44319611E+00 4 O(*) (adjust) O 1NI 1 0 0 293.00 5000.00 5000.00 1 1.00000000E-99 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 2 -2.66580549E+04 4.68860658E+00 1.00000000E-99 0.00000000E+00 0.00000000E+00 3 0.00000000E+00 0.00000000E+00-2.66580549E+04 4.68860658E+00 4 CO2(*) (adjust) C 1O 2NI 1 0 293.00 5000.00 5000.00 1 1.00000000E-99 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 2 -4.59500678E+04 2.14541635E+01 1.00000000E-99 0.00000000E+00 0.00000000E+00 3 0.00000000E+00 0.00000000E+00-4.59500678E+04 2.14541635E+01 4 HCO(*) (adjust) C 1H 1O 1NI 1 293.00 5000.00 5000.00 1 1.00000000E-99 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 2 -1.21882034E+04 1.49580180E+01 1.00000000E-99 0.00000000E+00 0.00000000E+00 3 0.00000000E+00 0.00000000E+00-1.21882034E+04 1.49580180E+01 4 C3H8(s) (adjust) C 3H 8Rh 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 C2H3(s) (adjust) C 2H 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 C3H7(s) (adjust) C 3H 7Rh 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 C3H6(s) (adjust) C 3H 6Rh 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 C3H8 120186C 3H 8 G 0300.00 5000.00 1000.00 1 0.07525217E+02 0.01889034E+00-0.06283924E-04 0.09179373E-08-0.04812410E-12 2 -0.16464548E+05-0.01784390E+03 0.08969208E+01 0.02668986E+00 0.05431425E-04 3 -0.02126000E-06 0.09243330E-10-0.13954918E+05 0.01935533E+03 4 COOH(s) C 1H 1O 2Rh 1I 300.00 3000.00 1000.00 1 0.30016165E+01 0.54084505E-02-0.40538058E-06-0.53422466E-09 0.11451887E-12 2 -0.32752722E+04-0.10965984E+02 0.12919217E+01 0.72675603E-02 0.98179476E-06 3 -0.20471294E-08 0.90832717E-13-0.25745610E+04-0.11983037E+01 4 END ! REACTIONS MWOFF KJOULES/MOLE H2 + Rh(s) + Rh(s) => H(s) + H(s) 3.000E-02 0.000 0.000 STICK O2 + Rh(s) + Rh(s) => O(s) + O(s) 1.000E-02 0.000 0.000 STICK H2O + Rh(s) => H2O(s) 1.000E-01 0.000 0.000 STICK CO2 + Rh(s) => CO2(s) 4.800E-02 0.000 0.000 STICK CO + Rh(s) => CO(s) 4.971E-01 0.000 0.000 STICK H(s) + H(s) => Rh(s) + Rh(s) + H2 5.574E+19 0.239 59.691 O(s) + O(s) => Rh(s) + Rh(s) + O2 5.329E+22 -0.137 386.995 H2O(s) => Rh(s) + H2O 6.858E+14 -0.280 44.993 CO(s) => Rh(s) + CO 1.300E+13 0.295 134.070 COV/CO(s) 0.000E+00 0.000 -47.000/ CO2(s) => Rh(s) + CO2 3.920E+11 0.315 20.505 O(s) + H(s) => OH(s) + Rh(s) 8.826E+21 -0.048 73.365 OH(s) + Rh(s) => O(s) + H(s) 1.000E+21 0.045 48.041 OH(s) + H(s) => H2O(s) + Rh(s) 1.743E+22 -0.127 41.731 H2O(s) + Rh(s) => OH(s) + H(s) 5.408E+22 0.129 98.220 OH(s) + OH(s) => O(s) + H2O(s) 5.736E+20 -0.081 121.594 O(s) + H2O(s) => OH(s) + OH(s) 1.570E+22 0.081 203.407 O(s) + C(s) => CO(s) + Rh(s) 1.173E+22 0.000 92.142 CO(s) + Rh(s) => O(s) + C(s) 6.390E+21 0.000 174.758 COV/CO(s) 0.000E+00 0.000 -47.000/ O(s) + CO(s) => CO2(s) + Rh(s) 6.183E+21 0.034 129.982 COV/CO(s) 0.000E+00 0.000 -47.000/ CO2(s) + Rh(s) => O(s) + CO(s) 5.752E+22 -0.175 106.492 CO(s) + OH(s) => COOH(s) + Rh(s) 2.922E+20 0.000 55.334 COV/CO(s) 0.000E+00 0.000 -47.000/ COOH(s) + Rh(s) => CO(s) + OH(s) 2.738E+21 0.000 48.375 COOH(s) + Rh(s) => CO2(s) + H(s) 1.165E+19 0.160 5.610 CO2(s) + H(s) => COOH(s) + Rh(s) 1.160E+20 -0.160 14.480 COOH(s) + H(s) => CO(s) + H2O(s) 5.999E+19 -0.188 33.552 CO(s) + H2O(s) => COOH(s) + H(s) 2.258E+19 0.051 97.078 COV/CO(s) 0.000E+00 0.000 -47.000/ CO(s) + OH(s) => CO2(s) + H(s) 3.070E+19 0.000 82.938 COV/CO(s) 0.000E+00 0.000 -47.000/ CO2(s) + H(s) => CO(s) + OH(s) 2.504E+21 -0.301 84.767 C(s) + OH(s) => CO(s) + H(s) 4.221E+20 0.078 30.038 CO(s) + H(s) => C(s) + OH(s) 3.244E+21 -0.078 138.262 COV/CO(s) 0.000E+00 0.000 -47.000/ END