!<><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><> ! ! H2/O2 oxidation reaction mechanism -- ! (c) Li, Zhao, Kazakov, and Dryer, Princeton University, 2003. ! !!!!!!!!!!!!!!!! IMPORTANT !!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! ! ! HOW TO USE THIS MECHANISM: ! ! Due to ! (1) limitations of CHEMKIN-II format (specifically, an inability to implement ! temperature-dependent collision efficiencies in falloff reactions) ! and ! (2) 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: ! ! Li, J., Zhao, Z., Kazakov, A., and Dryer, F.L. "An Updated Comprehensive Kinetic Model ! for H2 Combustion", Fall Technical Meeting of the Eastern States Section of the ! Combustion Institute, Penn State University, University Park, PA, October 26-29, 2003. ! ! ! HOW TO CONTACT THE AUTHORS: ! ! Prof. Frederick L. Dryer ! D-329-D Engineering Quadrangle ! Mechanical and Aerospace Engineering ! Princeton University ! Princeton, NJ 08544-5263 ! Phone: 609-258-5206 ! Lab: 609-258-0316 ! FAX: 609-258-1939 ! Email: fldryer@Princeton.EDU ! !********************************************************************************************** ! Development notes: ! !The following H2/O2 mechanism is based on Mueller et al's (Int.J.Chem.Kinet.1999,31:113) !Changes: ! !1.update the standard heat of formation of OH at 0K to 8.85kcal/mol (Ruscic et al, ! J. Phys. Chem. A, 2002, 106:2727) ! !2.update the rate constant of H+O2=O+OH as proposed by Hessler (J. Phys. Chem. A, 1998, ! 102:4517) ! !3.update the low-pressure-limit rate constant of H+O2(+M)=HO2(+M) with bath gases: H2, ! O2, N2, AR, HE, H2O as proposed by Michael et al (J. Phys. Chem. A, 2002,106:5297). ! The third-body efficiency of H2, O2, and H2O are taken as the average value over ! the temperature range of 300-3000K. ! The Fc in Troe's form with N2 and AR/HE as bath gas are different, so the fall-off ! kinetics is expressed in two sets, for N2 and AR/HE, respectively. ! !4.for all other recombination reactions, assume the third-body efficiency of HE is ! the same as AR. ! !5.modify the A factor of the rate constant of H+OH+M=H2O+M to 3.8E+22. ! !END OF NOTES !********************************************************************************************** ELEMENTS H O N C AR HE END SPECIES H2 O2 H2O H O OH HO2 H2O2 AR N2 HE CO CO2 END THERMO ALL 300.0 1000.0 5000.0 H 120186H 1 G 0300.00 5000.00 1000.00 1 2.50000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 2 2.54716270E+04-4.60117638E-01 2.50000000E+00 0.00000000E+00 0.00000000E+00 3 0.00000000E+00 0.00000000E+00 2.54716270E+04-4.60117608E-01 4 O 120186O 1 G 0300.00 5000.00 1000.00 1 2.54205966E+00-2.75506191E-05-3.10280335E-09 4.55106742E-12-4.36805150E-16 2 2.92308027E+04 4.92030811E+00 2.94642878E+00-1.63816649E-03 2.42103170E-06 3 -1.60284319E-09 3.89069636E-13 2.91476445E+04 2.96399498E+00 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 H2 121286H 2 G 0300.00 5000.00 1000.00 1 2.99142337E+00 7.00064411E-04-5.63382869E-08-9.23157818E-12 1.58275179E-15 2 -8.35033997E+02-1.35511017E+00 3.29812431E+00 8.24944174E-04-8.14301529E-07 3 -9.47543433E-11 4.13487224E-13-1.01252087E+03-3.29409409E+00 4 O2 121386O 2 G 0300.00 5000.00 1000.00 1 3.69757819E+00 6.13519689E-04-1.25884199E-07 1.77528148E-11-1.13643531E-15 2 -1.23393018E+03 3.18916559E+00 3.21293640E+00 1.12748635E-03-5.75615047E-07 3 1.31387723E-09-8.76855392E-13-1.00524902E+03 6.03473759E+00 4 H2O 20387H 2O 1 G 0300.00 5000.00 1000.00 1 2.67214561E+00 3.05629289E-03-8.73026011E-07 1.20099639E-10-6.39161787E-15 2 -2.98992090E+04 6.86281681E+00 3.38684249E+00 3.47498246E-03-6.35469633E-06 3 6.96858127E-09-2.50658847E-12-3.02081133E+04 2.59023285E+00 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 4.57316685E+00 4.33613639E-03-1.47468882E-06 2.34890357E-10-1.43165356E-14 2 -1.80069609E+04 5.01136959E-01 3.38875365E+00 6.56922581E-03-1.48501258E-07 3 -4.62580552E-09 2.47151475E-12-1.76631465E+04 6.78536320E+00 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 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 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 H+O2=O+OH 3.547e+15 -0.406 1.6599E+4 O+H2=H+OH 0.508E+05 2.67 0.629E+04 H2+OH=H2O+H 0.216E+09 1.51 0.343E+04 O+H2O=OH+OH 2.97e+06 2.02 1.34e+4 H2+M=H+H+M 4.577E+19 -1.40 1.0438E+05 H2/2.5/ H2O/12.0/ CO/1.9/ CO2/3.8/ AR/0.0/ HE/0.0/ H2+AR=H+H+AR 5.84e18 -1.1 1.0438E+05 H2+HE=H+H+HE 5.84e18 -1.1 1.0438E+05 O+O+M=O2+M 6.165E+15 -0.50 0.000E+00 H2/2.5/ H2O/12.0/ AR/0.0/ HE/0.0/ CO/1.9/ CO2/3.8/ 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 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/ H+OH+M=H2O+M 3.800E+22 -2.00 0.000E+00 H2/2.5/ H2O/12./ AR/0.38/ HE/0.38/ CO/1.9/ CO2/3.8/ H+O2(+M)=HO2(+M) 1.475E+12 0.60 0.00E+00 LOW/6.366E+20 -1.72 5.248E+02/ TROE/0.8 1E-30 1E+30/ H2/2.0/ H2O/11./ O2/0.78/ CO/1.9/ CO2/3.8/ HO2+H=H2+O2 1.66E+13 0.00 0.823E+03 HO2+H=OH+OH 7.079E+13 0.00 2.95E+02 HO2+O=O2+OH 0.325E+14 0.00 0.00E+00 HO2+OH=H2O+O2 2.890E+13 0.00 -4.970E+02 HO2+HO2=H2O2+O2 4.200e+14 0.00 1.1982e+04 HO2+HO2=H2O2+O2 1.300e+11 0.00 -1.6293e+3 H2O2(+M)=OH+OH(+M) 2.951e+14 0.00 4.843E+04 LOW/1.202E+17 0.00 4.55E+04/ TROE/0.5 1E-30 1E+30/ H2/2.5/ H2O/12./ CO/1.9/ CO2/3.8/ AR/0.64/ HE/0.64/ H2O2+H=H2O+OH 0.241E+14 0.00 0.397E+04 H2O2+H=HO2+H2 0.482E+14 0.00 0.795E+04 H2O2+O=OH+HO2 9.550E+06 2.00 3.970E+03 H2O2+OH=HO2+H2O 1.000E+12 0.00 0.00 H2O2+OH=HO2+H2O 5.800E+14 0.00 9.557E+03 END