!<><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><>! ! ! ----- H2 Kinetic Mechanism ----- ! ----- Version 6-10-2011 ----- ! ! (c) Burke, Chaos, Ju, Dryer, and Klippenstein; Princeton University, 2011. ! ! !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! IMPORTANT !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! IMPORTANT !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! IMPORTANT !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! ! ! HOW TO USE THIS MECHANISM: ! ! (*) Due to limitations of CHEMKIN-II format (specifically, an inability to ! implement temperature-dependent collision efficiencies in falloff ! reactions) and the lack of fundamental understanding of the mixing rules ! for the falloff reactions with the bath gases that have different ! broadening factors, the present implementation represents a compromise ! (approximate) formulation. As a consequence, ! ! PRIOR TO ITS USE IN THE CALCULATIONS, THIS FILE HAS TO BE MODIFIED. ! DEPENDING ON WHAT BATH GAS (DILUTANT) IS MOST ABUNDANT IN YOUR SYSTEM ! (THE PRESENT CHOICES ARE N2, AR, OR HE), YOU SHOULD UNCOMMENT THE ! CORRESPONDING BLOCK FOR THE REACTION H+O2(+M)=HO2(+M), AND COMMENT THE ! BLOCK FOR OTHER DILUTANT(S). AS GIVEN, THE MAIN DILUTANT IS SET TO BE N2. ! ! ! HOW TO REFERENCE THIS MECHANISM: ! ! M.P. Burke, M. Chaos, Y. Ju, F.L. Dryer, S.J. Klippenstein ! "Comprehensive H2/O2 Kinetic Model for High-Pressure Combustion," ! Int. J. Chem. Kinet. 44 (2012) 444-474. ! ! ! ! HOW TO CONTACT THE AUTHORS: ! ! Prof. Michael P. Burke ! Email: mpburke@columbia.edu ! ! Prof. Frederick L. Dryer ! Email: fldryer@princeton.edu ! ! !<><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><>! ! ELEMENTS H O N AR HE C END SPECIES H H2 O OH H2O O2 HO2 H2O2 N2 AR HE CO CO2 END !********************************************************************************* THERMO ALL 0300.00 1000.00 5000.00 H 120186H 1 G 0300.00 5000.00 1000.00 1 0.02500000E+02 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 2 0.02547163E+06-0.04601176E+01 0.02500000E+02 0.00000000E+00 0.00000000E+00 3 0.00000000E+00 0.00000000E+00 0.02547163E+06-0.04601176E+01 4 H2 121286H 2 G 0300.00 5000.00 1000.00 1 0.02991423E+02 0.07000644E-02-0.05633829E-06-0.09231578E-10 0.01582752E-13 2 -0.08350340E+04-0.01355110E+02 0.03298124E+02 0.08249442E-02-0.08143015E-05 3 -0.09475434E-09 0.04134872E-11-0.01012521E+05-0.03294094E+02 4 O 120186O 1 G 0300.00 5000.00 1000.00 1 0.02542060E+02-0.02755062E-03-0.03102803E-07 0.04551067E-10-0.04368052E-14 2 0.02923080E+06 0.04920308E+02 0.02946429E+02-0.01638166E-01 0.02421032E-04 3 -0.01602843E-07 0.03890696E-11 0.02914764E+06 0.02963995E+02 4 OH S 9/01O 1H 1 0 0G 200.000 6000.000 1000. 1 2.86472886E+00 1.05650448E-03-2.59082758E-07 3.05218674E-11-1.33195876E-15 2 3.68362875E+03 5.70164073E+00 4.12530561E+00-3.22544939E-03 6.52764691E-06 3 -5.79853643E-09 2.06237379E-12 3.34630913E+03-6.90432960E-01 4.51532273E+03 4 H2O 20387H 2O 1 G 0300.00 5000.00 1000.00 1 0.02672146E+02 0.03056293E-01-0.08730260E-05 0.01200996E-08-0.06391618E-13 2 -0.02989921E+06 0.06862817E+02 0.03386842E+02 0.03474982E-01-0.06354696E-04 3 0.06968581E-07-0.02506588E-10-0.03020811E+06 0.02590233E+02 4 O2 121386O 2 G 0300.00 5000.00 1000.00 1 0.03697578E+02 0.06135197E-02-0.01258842E-05 0.01775281E-09-0.01136435E-13 2 -0.01233930E+05 0.03189166E+02 0.03212936E+02 0.01127486E-01-0.05756150E-05 3 0.01313877E-07-0.08768554E-11-0.01005249E+05 0.06034738E+02 4 HO2 L 5/89H 1O 2 00 00G 200.000 3500.000 1000.000 1 4.01721090E+00 2.23982013E-03-6.33658150E-07 1.14246370E-10-1.07908535E-14 2 1.11856713E+02 3.78510215E+00 4.30179801E+00-4.74912051E-03 2.11582891E-05 3 -2.42763894E-08 9.29225124E-12 2.94808040E+02 3.71666245E+00 1.00021620E+04 4 H2O2 120186H 2O 2 G 0300.00 5000.00 1000.00 1 0.04573167E+02 0.04336136E-01-0.01474689E-04 0.02348904E-08-0.01431654E-12 2 -0.01800696E+06 0.05011370E+01 0.03388754E+02 0.06569226E-01-0.01485013E-05 3 -0.04625806E-07 0.02471515E-10-0.01766315E+06 0.06785363E+02 4 N2 121286N 2 G 0300.00 5000.00 1000.00 1 0.02926640E+02 0.01487977E-01-0.05684761E-05 0.01009704E-08-0.06753351E-13 2 -0.09227977E+04 0.05980528E+02 0.03298677E+02 0.01408240E-01-0.03963222E-04 3 0.05641515E-07-0.02444855E-10-0.01020900E+05 0.03950372E+02 4 AR 120186AR 1 G 0300.00 5000.00 1000.00 1 0.02500000E+02 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 2 -0.07453750E+04 0.04366001E+02 0.02500000E+02 0.00000000E+00 0.00000000E+00 3 0.00000000E+00 0.00000000E+00-0.07453750E+04 0.04366001E+02 4 HE 120186HE 1 G 0300.00 5000.00 1000.00 1 0.02500000E+02 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 2 -0.07453750E+04 0.09153489E+01 0.02500000E+02 0.00000000E+00 0.00000000E+00 3 0.00000000E+00 0.00000000E+00-0.07453750E+04 0.09153488E+01 4 CO 121286C 1O 1 G 0300.00 5000.00 1000.00 1 0.03025078E+02 0.01442689E-01-0.05630828E-05 0.01018581E-08-0.06910952E-13 2 -0.01426835E+06 0.06108218E+02 0.03262452E+02 0.01511941E-01-0.03881755E-04 3 0.05581944E-07-0.02474951E-10-0.01431054E+06 0.04848897E+02 4 CO2 121286C 1O 2 G 0300.00 5000.00 1000.00 1 0.04453623E+02 0.03140169E-01-0.01278411E-04 0.02393997E-08-0.01669033E-12 2 -0.04896696E+06-0.09553959E+01 0.02275725E+02 0.09922072E-01-0.01040911E-03 3 0.06866687E-07-0.02117280E-10-0.04837314E+06 0.01018849E+03 4 END !********************************************************************************* REACTIONS !====================== !H2-O2 Chain Reactions !====================== ! Hong et al., Proc. Comb. Inst. 33:309-316 (2011) H+O2 = O+OH 1.04E+14 0.00 1.5286E+04 ! Baulch et al., J. Phys. Chem. Ref. Data, 21:411 (1992) O+H2 = H+OH 3.818E+12 0.00 7.948E+03 DUPLICATE O+H2 = H+OH 8.792E+14 0.00 1.917E+04 DUPLICATE ! Michael and Sutherland, J. Phys. Chem. 92:3853 (1988) H2+OH = H2O+H 0.216E+09 1.51 0.343E+04 ! Baulch et al., J. Phys. Chem. Ref. Data, 21:411 (1992) OH+OH = O+H2O 3.34E+04 2.42 -1.93E+03 !============================ !H2-O2 Dissociation Reactions !============================ ! Tsang and Hampson, J. Phys. Chem. Ref. Data, 15:1087 (1986) H2+M = H+H+M 4.577E+19 -1.40 1.0438E+05 H2/2.5/ H2O/12/ CO/1.9/ CO2/3.8/ AR/0.0/ HE/0.0/ ! Tsang and Hampson, J. Phys. Chem. Ref. Data, 15:1087 (1986) H2+AR = H+H+AR 5.840E+18 -1.10 1.0438E+05 H2+HE = H+H+HE 5.840E+18 -1.10 1.0438E+05 ! Tsang and Hampson, J. Phys. Chem. Ref. Data, 15:1087 (1986) O+O+M = O2+M 6.165E+15 -0.50 0.000E+00 H2/2.5/ H2O/12/ AR/0.0/ HE/0.0/ CO/1.9/ CO2/3.8/ ! Tsang and Hampson, J. Phys. Chem. Ref. Data, 15:1087 (1986) O+O+AR = O2+AR 1.886E+13 0.00 -1.788E+03 O+O+HE = O2+HE 1.886E+13 0.00 -1.788E+03 ! Tsang and Hampson, J. Phys. Chem. Ref. Data, 15:1087 (1986) O+H+M = OH+M 4.714E+18 -1.00 0.000E+00 H2/2.5/ H2O/12/ AR/0.75/ HE/0.75/ CO/1.9/ CO2/3.8/ ! Srinivasan and Michael, Int. J. Chem. Kinetic. 38 (2006) ! Rate constant is for Ar with efficiencies from Michael et al., J. Phys. Chem. A, 106 (2002) H2O+M = H+OH+M 6.064E+27 -3.322 1.2079E+05 H2/3.0/ H2O/0.0/ HE/1.10/ N2/2.00/ O2/1.5/ ! Efficiencies for CO and CO2 taken from Li et al., Int. J. Chem. Kinet. 36:566-575 (2004) CO/1.9/ CO2/3.8/ ! Srinivasan and Michael, Int. J. Chem. Kinetic. 38 (2006) H2O+H2O = H+OH+H2O 1.006E+26 -2.44 1.2018E+05 !================================= ! Formation and consumption of HO2 !================================= ! High-pressure limit from Troe, Proc. Comb. Inst. 28:1463-1469 (2000) ! Low-pressure limit from Michael et al., J. Phys. Chem. A 106:5297-5313 ! Centering factors from Fernandes et al., Phys. Chem. Chem. Phys. 10:4313-4321 (2008) !================================================================================= ! MAIN BATH GAS IS N2 (comment this reaction otherwise) ! H+O2(+M) = HO2(+M) 4.65084E+12 0.44 0.000E+00 LOW/6.366E+20 -1.72 5.248E+02/ TROE/0.5 1E-30 1E+30/ H2/2.0/ H2O/14/ O2/0.78/ CO/1.9/ CO2/3.8/ AR/0.67/ HE/0.8/ !================================================================================= ! MAIN BATH GAS IS AR OR HE (comment this reaction otherwise) ! !H+O2(+M) = HO2(+M) 4.65084E+12 0.44 0.000E+00 ! LOW/9.042E+19 -1.50 4.922E+02/ ! TROE/0.5 1E-30 1E+30/ ! H2/3.0/ H2O/21/ O2/1.1/ CO/2.7/ CO2/5.4/ HE/1.2/ N2/1.5/ !================================================================================= ! Michael et al., Proc. Comb. Inst. 28:1471 (2000) !HO2+H = H2+O2 3.659E+06 2.09 -1.451E+03 !Scaled by 0.75 HO2+H = H2+O2 2.750E+06 2.09 -1.451E+03 ! Mueller et al., Int. J. Chem. Kinetic. 31:113 (1999) HO2+H = OH+OH 7.079E+13 0.00 2.950E+02 ! Fernandez-Ramos and Varandas, J. Phys. Chem. A 106:4077-4083 (2002) !HO2+O = O2+OH 4.750E+10 1.00 -7.2393E+02 !Scaled by 0.60 HO2+O = O2+OH 2.850E+10 1.00 -7.2393E+02 ! Keyser, J. Phys. Chem. 92:1193 (1988) HO2+OH = H2O+O2 2.890E+13 0.00 -4.970E+02 !===================================== !Formation and Consumption of H2O2 !===================================== ! Hippler et al., J. Chem. Phys. 93:1755 (1990) HO2+HO2 = H2O2+O2 4.200E+14 0.00 1.1982E+04 DUPLICATE HO2+HO2 = H2O2+O2 1.300E+11 0.00 -1.6293E+03 DUPLICATE ! Troe, Combust. Flame, 158:594-601 (2011) ! Rate constant is for Ar H2O2(+M) = OH+OH(+M) 2.00E+12 0.90 4.8749E+04 LOW/2.49E+24 -2.30 4.8749E+04/ TROE/0.43 1E-30 1E+30/ H2O/7.5/ CO2/1.6/ N2/1.5/ O2/1.2/ HE/0.65/ H2O2/7.7/ ! Efficiencies for H2 and CO taken from Li et al., Int. J. Chem. Kinet. 36:566-575 (2004) H2/3.7/ CO/2.8/ ! Tsang and Hampson, J. Phys. Chem. Ref. Data, 15:1087 (1986) H2O2+H = H2O+OH 2.410E+13 0.00 3.970E+03 H2O2+H = HO2+H2 4.820E+13 0.00 7.950E+03 H2O2+O = OH+HO2 9.550E+06 2.00 3.970E+03 ! Hong et al., J. Phys. Chem. A 114 (2010) 5718�5727 H2O2+OH = HO2+H2O 1.740E+12 0.00 3.180E+02 DUPLICATE H2O2+OH = HO2+H2O 7.590E+13 0.00 7.270E+03 DUPLICATE END