---------------------------------------------------------------------! !*********************************************************************** !**** * !**** C3H6-NO-CO-CO2-O2 SURFACE MECHANISM ON Pt/Rh * !**** * !**** D. Chatterjee, O. Deutschmann, J. Warnatz * !**** Heidelberg University, Germany * !**** Contact: O. Deutschmann, mail@detchem.com * !**** * !**** * !**** Reference: * !**** (1) D. Chatterjee, O. Deutschmann, J. Warnatz. * !**** Detailed surface reaction mechanism in a three-way * !**** catalyst. Faraday Discussions 119 (2001) 371-384 * !**** * !**** SURFACE CHEMKIN format * !**** * !**** Kinetic data: * !**** k = A * T**b * exp (-Ea/RT) A b Ea * !**** (cm,mol,s) - kJ/mol * !**** * !**** * !**** * !**** There are three different kinds of adsorption sites: * !**** Pt(S) nucleophilic = (S) !**** Pt(S) electrophilic = (S2) * !**** Rh(S1) = (S1) !**** The total surface is made of 75% Pt and 25% Rh, i.e. * !**** the initial coverage must be 0.75 (S) amd 0.25 (S1). * !**** * !**** The mechanism is valid only for this Pt/Rh ratio!!! * !**** In particular, the coverage dependent activation energies * !**** are scaled for that ratio! * !**** * !*********************************************************************** SITE/SURFACE/ SDEN/2.72E-9/ Pt(S) O(S) C3H6(S)/2/ H(S) H2O(S) CO2(S) CO(S) NO(S) N(S) C3H5(S) C2H3(S) CH2(S) CH3(S) OH(S) CH(S) C(S) C3H5(S2) C3H4(S2) C3H3(S2) C2H2(S2) CH(S2) CHO(S) C2H3O(S) Rh(S1) O(S1) CO(S1) NO(S1) N(S1) END THERMO ALL 300.0 1000.0 3000.0 O(S) 92491O 1Pt 1 I 300.00 3000.00 1000.00 1 0.19454180E+01 0.91761647E-03-0.11226719E-06-0.99099624E-10 0.24307699E-13 2 -0.14005187E+05-0.11531663E+02-0.94986904E+00 0.74042305E-02-0.10451424E-05 3 -0.61120420E-08 0.33787992E-11-0.13209912E+05 0.36137905E+01 4 O2(S) 92491O 2Pt 1 I 300.00 3000.00 1000.00 1 0.35989249E+01 0.20437732E-02-0.23878221E-06-0.22041054E-09 0.53299430E-13 2 -0.41095444E+04-0.21604582E+02-0.20174649E+01 0.14146218E-01-0.16376665E-05 3 -0.11264421E-07 0.60101386E-11-0.25084473E+04 0.79811935E+01 4 H(S) 92491H 1Pt 1 I 300.00 3000.00 1000.00 1 0.10696996E+01 0.15432230E-02-0.15500922E-06-0.16573165E-09 0.38359347E-13 2 -0.50546128E+04-0.71555238E+01-0.13029877E+01 0.54173199E-02 0.31277972E-06 3 -0.32328533E-08 0.11362820E-11-0.42277075E+04 0.58743238E+01 4 H2(S) 92491H 2Pt 1 I 300.00 3000.00 1000.00 1 0.15330955E+01 0.34586885E-02-0.32622225E-06-0.36824219E-09 0.83855205E-13 2 -0.36401533E+04-0.10822206E+02-0.21517782E+01 0.87039210E-02 0.11154106E-05 3 -0.42477102E-08 0.96133203E-12-0.22640681E+04 0.97397461E+01 4 H2O(S) 92491O 1H 2Pt 1 I 300.00 3000.00 1000.00 1 0.25803051E+01 0.49570827E-02-0.46894056E-06-0.52633137E-09 0.11998322E-12 2 -0.38302234E+05-0.17406322E+02-0.27651553E+01 0.13315115E-01 0.10127695E-05 3 -0.71820083E-08 0.22813776E-11-0.36398055E+05 0.12098145E+02 4 OH(S) 92491O 1H 1Pt 1 I 300.00 3000.00 1000.00 1 0.18249973E+01 0.32501565E-02-0.31197541E-06-0.34603206E-09 0.79171472E-13 2 -0.26685492E+05-0.12280891E+02-0.20340881E+01 0.93662683E-02 0.66275214E-06 3 -0.52074887E-08 0.17088735E-11-0.25319949E+05 0.89863186E+01 4 Pt(S) Pt 1 S 300.0 3000.0 1000.0 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) 0C 1O 1Pt 1 I 300.00 3000.00 1000.00 1 0.47083778E+01 0.96037297E-03-0.11805279E-06-0.76883826E-10 0.18232000E-13 2 -0.32311723E+05-0.16719593E+02 0.48907466E+01 0.68134235E-04 0.19768814E-06 3 0.12388669E-08-0.90339249E-12-0.32297836E+05-0.17453161E+02 4 CO2(S) 081292C 1O 2Pt 1 I 300.00 3000.00 1000.00 1 0.46900000E+00 0.62660000E-02 0.00000000E-00 0.00000000E-00 0.00000000E-00 2 -0.50458700E+05-0.45550000E+01 0.46900000E+00 0.62662000E-02 0.00000000E-00 3 0.00000000E-00 0.00000000E-00-0.50458700E+05-0.45550000E+01 4 C(S) 0C 1Pt 1 I 300.00 3000.00 1000.00 1 0.15792824E+01 0.36528701E-03-0.50657672E-07-0.34884855E-10 0.88089699E-14 2 0.99535752E+04-0.30240495E+01 0.58924019E+00 0.25012842E-02-0.34229498E-06 3 -0.18994346E-08 0.10190406E-11 0.10236923E+05 0.21937017E+01 4 CH(S) 0C 1H 1Pt 1 I 300.00 3000.00 1000.00 1 -0.48242472E-02 0.30446239E-02-0.16066099E-06-0.29041700E-09 0.57999924E-13 2 0.22595219E+05 0.56677818E+01 0.84157485E+00 0.13095380E-02 0.28464575E-06 3 0.63862904E-09-0.42766658E-12 0.22332801E+05 0.11452305E+01 4 CH2(S) 0C 1H 2Pt 1 I 300.00 3000.00 1000.00 1 0.74076122E+00 0.48032533E-02-0.32825633E-06-0.47779786E-09 0.10073452E-12 2 0.10443752E+05 0.40842086E+00-0.14876404E+00 0.51396289E-02 0.11211075E-05 3 -0.82755452E-09-0.44572345E-12 0.10878700E+05 0.57451882E+01 4 CH3(S) 0C 1H 3Pt 1 I 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 C3H6(S) C 3H 6Pt 2 I 300.0 3000.0 1000.0 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 C3H5(S) C 3H 5Pt 1 I 300.0 3000.0 1000.0 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) C 2H 3Pt 1 I 300.0 3000.0 1000.0 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 NO(S) N 1O 1Pt 1 I 300.0 3000.0 1000.0 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 N(S) N 1Pt 1 0 I 300.0 3000.0 1000. 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 NO2(S) N 1O 2Pt 1 I 300.0 3000.0 1000.0 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(S1) Rh 1 S 300.0 3000.0 1000.0 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 NO(S1) N 1O 1Rh 1 I 300.0 3000.0 1000.0 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(S1) 0C 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 O(S1) 92491O 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 N(S1) 92491N 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 C3H5(S2) C 3H 5Pt 1 I 300.0 3000.0 1000.0 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 C3H4(S2) C 3H 4Pt 1 I 300.0 3000.0 1000.0 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 C3H3(S2) C 3H 3Pt 1 I 300.0 3000.0 1000.0 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 C2H2(S2) C 2H 2Pt 1 I 300.0 3000.0 1000.0 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(S2) C 1H 1Pt 1 I 300.0 3000.0 1000.0 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 CHO(S) C 1H 1O 1Pt 1I 300.0 3000.0 1000.0 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 C2H3O(S) C 2H 3O 1Pt 1I 300.0 3000.0 1000.0 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 KJOULES/MOL !********************************************************************* !**** C3H6/O2/NO/Pt Subsystem * !********************************************************************* !********************************************************************* !**** 1. ADSORPTION !********************************************************************* O2 +Pt(S) +Pt(S) =>O(S) +O(S) 7.000E-02 0.0 0.0 STICK C3H6 +Pt(S) +Pt(S) =>C3H6(S) 9.800E-01 0.0 0.0 STICK C3H6 +O(S) +Pt(S) =>C3H5(S2)+OH(S) 5.000E-02 0.0 0.0 FORD/Pt(S) 1/ STICK H2 +Pt(S) +Pt(S) =>H(S) +H(S) 4.458E-02 0.0 0.0 FORD/Pt(S) 1/ STICK H2O +Pt(S) =>H2O(S) 7.500E-01 0.0 0.0 STICK CO2 +Pt(S) =>CO2(S) 5.000E-03 0.0 0.0 STICK CO +Pt(S) =>CO(S) 8.400E-01 0.0 0.0 STICK NO +Pt(S) =>NO(S) 8.500E-01 0.0 0.0 STICK !********************************************************************* !**** 2. DESORPTION !********************************************************************* O(S) +O(S) =>Pt(S) +Pt(S) +O2 3.700E+21 0.0 232.0 COV/O(S) 0.0 0.0 -90.0/ C3H6(S) =>C3H6 +Pt(S) +Pt(S) 1.000E+13 0.0 72.7 C3H5(S2)+OH(S) =>C3H6 +O(S) +Pt(S) 3.700E+21 0.0 31.0 H(S) +H(S) =>H2 +Pt(S) +Pt(S) 3.700E+21 0.0 67.4 COV/H(S) 0.0 0.0 -6.0/ H2O(S) =>Pt(S) +H2O 1.000E+13 0.0 40.3 CO(S) =>CO +Pt(S) 1.000E+13 0.0 136.4 COV/CO(S) 0.0 0.0 -33.0/ CO2(S) =>CO2 +Pt(S) 1.000E+13 0.0 27.1 NO(S) =>NO +Pt(S) 1.000E+16 0.0 140.0 N(S) +N(S) =>N2 +Pt(S) +Pt(S) 3.700E+21 0.0 113.9 COV/CO(S) 0.0 0.0 -75.0/ !********************************************************************* !**** 3. SURFACE REACTIONS !********************************************************************* C3H5(S2)+O(S) =>C3H4(S2)+OH(S) 3.700E+21 0.0 95.0 C3H4(S2)+O(S) =>C3H3(S2)+OH(S) 3.700E+21 0.0 00.0 C3H3(S2)+O(S) =>C2H2(S2)+CHO(S) 1.360E+40 0.0 00.0 CHO(S) +Pt(S) =>OH(S) +C(S) 1.360E+40 0.0 00.0 C2H2(S2)+O(S) =>CHO(S) +CH(S2) 1.360E+40 0.0 00.0 CH(S2) +O(S) =>OH(S) +C(S) 3.700E+40 0.0 00.0 C3H6(S) =>C3H5(S) +H(S) 1.000E+13 0.0 75.4 C3H5(S) +H(S) =>C3H6(S) 3.700E+21 0.0 48.8 C3H5(S) +Pt(S) =>C2H3(S) +CH2(S) 3.700E+21 0.0 108.2 C2H3(S) +CH2(S) =>C3H5(S) +Pt(S) 3.700E+21 0.0 3.2 C2H3(S) +Pt(S) =>CH3(S) +C(S) 3.700E+21 0.0 46.0 CH3(S) +C(S) =>C2H3(S) +Pt(S) 3.700E+21 0.0 46.9 CH3(S) +O(S) =>CH2(S) +OH(S) 3.700E+21 0.0 36.6 CH2(S) +OH(S) =>CH3(S) +O(S) 3.700E+21 0.0 25.1 CH2(S) +O(S) =>CH(S) +OH(S) 3.700E+21 0.0 25.1 CH(S) +OH(S) =>CH2(S) +O(S) 3.700E+21 0.0 25.2 CH(S) +O(S) =>C(S) +OH(S) 3.700E+21 0.0 25.1 C(S) +OH(S) =>CH(S) +O(S) 3.700E+21 0.0 224.8 O(S) +H(S) =>OH(S) +Pt(S) 3.700E+21 0.0 11.5 OH(S) +Pt(S) =>O(S) +H(S) 5.770E+22 0.0 74.9 H(S) +OH(S) =>H2O(S) +Pt(S) 3.700E+21 0.0 17.4 H2O(S) +Pt(S) =>H(S) +OH(S) 3.760E+21 0.0 73.6 OH(S) +OH(S) =>H2O(S) +O(S) 3.700E+21 0.0 48.2 H2O(S) +O(S) =>OH(S) +OH(S) 2.350E+20 0.0 41.0 CO(S) +O(S) =>CO2(S) +Pt(S) 3.700E+20 0.0 108.0 COV/CO(S) 0.0 0.0 -33.0/ COV/NO(S) 0.0 0.0 +90.0/ CO2(S) +Pt(S) =>CO(S) +O(S) 3.700E+21 0.0 165.1 COV/O(S) 0.0 0.0 +45.0/ C(S) +O(S) =>CO(S) +Pt(S) 3.700E+21 0.0 0.0 COV/CO(S) 0.0 0.0 +33.0/ CO(S) +Pt(S) =>C(S) +O(S) 3.700E+21 0.0 218.5 COV/O(S) 0.0 0.0 +45.0/ NO(S) +Pt(S) =>N(S) +O(S) 5.000E+20 0.0 107.8 COV/CO(S) 0.0 0.0 +3.0/ N(S) +O(S) =>NO(S) +Pt(S) 3.700E+21 0.0 128.1 COV/O(S) 0.0 0.0 -45.0/ C2H3(S) +O(S) =>C2H3O(S)+Pt(S) 3.700E+19 0.0 62.3 C2H3O(S)+Pt(S) =>C2H3(S) +O(S) 3.700E+21 0.0 196.7 COV/O(S) 0.0 0.0 +45.0/ !********************************************************************* !**** NO/CO/CO2/Rh Subsystem * !********************************************************************* !**** 1. ADSORPTION !********************************************************************* O2 +Rh(S1) +Rh(S1) =>O(S1) +O(S1) 1.000E-02 0.5 0.0 FORD/Rh(S1) 1/ STICK CO +Rh(S1) =>CO(S1) 5.000E-01 0.0 0.0 STICK NO +Rh(S1) =>NO(S1) 5.000E-01 0.0 0.0 STICK !********************************************************************* !**** 2. DESORPTION !********************************************************************* O(S1) +O(S1) =>O2 +Rh(S1) +Rh(S1) 3.000E+21 0.0 293.3 CO(S1) =>CO +Rh(S1) 1.000E+14 0.0 132.3 COV/N(S1) 0.0 0.0 -41.9/ COV/CO(S1) 0.0 0.0 -18.8/ NO(S1) =>NO +Rh(S1) 5.000E+13 0.0 108.9 N(S1) +N(S1) =>N2 +Rh(S1) +Rh(S1) 1.110E+19 0.0 136.9 COV/N(S1) 0.0 0.0 -16.7/ CO(S1) +O(S1) =>CO2 +Rh(S1) +Rh(S1) 3.700E+20 0.0 59.9 !********************************************************************* !**** 3. NO(Rh) SURFACE REACTIONS !********************************************************************* NO(S1) +Rh(S1) =>N(S1) +O(S1) 2.220E+22 0.0 79.5 !********************************************************************* END !*********************************************************************