""" ============================================================================ | NUI Galway - Combustion Chemistry Centre H2/CO mechanism | | A. KEROMNES, W. K. METCALFE, S. BURKE, H. J. CURRAN | | September 2012 | ============================================================================ --------------------------- How to cite ------------------------------- An experimental and detailed chemical kinetic modeling study of hydrogen and syngas mixture oxidation at elevated pressures A. Keromnes, W.K. Metcalfe, K.A. Heufer, N. Donohoe, A.K. Das, C-J Sung, J. Herzler, C. Naumann, P. Griebel, O. Mathieu, M.C. Krejci, E.L. Petersen, W.J. Pitz, H.J. Curran Combust. Flame (2013), http://dx.doi.org/10.1016/j.combustflame.2013.01.001 Combustion and Flame 160 (2013) 9951011 ----------------------------------------------------------------------------- ============================================================================ | NUI Galway - Combustion Chemistry Centre H2/CO mechanism | | A. KEROMNES, W. K. METCALFE, S. BURKE, H. J. CURRAN | | September 2012 | ============================================================================ --------------------------- How to cite ------------------------------- An experimental and detailed chemical kinetic modeling study of hydrogen and syngas mixture oxidation at elevated pressures A. Keromnes, W.K. Metcalfe, K.A. Heufer, N. Donohoe, A.K. Das, C-J Sung, J. Herzler, C. Naumann, P. Griebel, O. Mathieu, M.C. Krejci, E.L. Petersen, W.J. Pitz, H.J. Curran Combust. Flame (2013), http://dx.doi.org/10.1016/j.combustflame.2013.01.001 Combustion and Flame 160 (2013) 9951011 ----------------------------------------------------------------------------- """ units(length='cm', time='s', quantity='mol', act_energy='cal/mol') ideal_gas(name='gas', elements="C H N O Ar He", species="""H H2 O O2 OH OH* H2O N2 HO2 H2O2 AR CO CO2 HE HCO""", reactions='all', transport='Mix', initial_state=state(temperature=300.0, pressure=OneAtm)) #------------------------------------------------------------------------------- # Species data #------------------------------------------------------------------------------- species(name='H', atoms='H:1', thermo=(NASA([200.00, 1000.00], [ 2.50000000E+00, 0.00000000E+00, 0.00000000E+00, 0.00000000E+00, 0.00000000E+00, 2.54736600E+04, -4.46682850E-01]), NASA([1000.00, 6000.00], [ 2.50000000E+00, 0.00000000E+00, 0.00000000E+00, 0.00000000E+00, 0.00000000E+00, 2.54736600E+04, -4.46682850E-01])), transport=gas_transport(geom='atom', diam=2.05, well_depth=145.0), note='L6/94') species(name='H2', atoms='H:2', thermo=(NASA([300.00, 1000.00], [ 3.29812400E+00, 8.24944200E-04, -8.14301500E-07, -9.47543400E-11, 4.13487200E-13, -1.01252100E+03, -3.29409400E+00]), NASA([1000.00, 5000.00], [ 2.99142300E+00, 7.00064400E-04, -5.63382900E-08, -9.23157800E-12, 1.58275200E-15, -8.35034000E+02, -1.35511000E+00])), transport=gas_transport(geom='linear', diam=2.92, well_depth=38.0, polar=0.79, rot_relax=280.0), note='121286') species(name='O', atoms='O:1', thermo=(NASA([300.00, 1000.00], [ 2.94642900E+00, -1.63816600E-03, 2.42103200E-06, -1.60284300E-09, 3.89069600E-13, 2.91476400E+04, 2.96399500E+00]), NASA([1000.00, 5000.00], [ 2.54206000E+00, -2.75506200E-05, -3.10280300E-09, 4.55106700E-12, -4.36805200E-16, 2.92308000E+04, 4.92030800E+00])), transport=gas_transport(geom='atom', diam=2.75, well_depth=80.0), note='120186') species(name='O2', atoms='O:2', thermo=(NASA([300.00, 1000.00], [ 3.21293600E+00, 1.12748600E-03, -5.75615000E-07, 1.31387700E-09, -8.76855400E-13, -1.00524900E+03, 6.03473800E+00]), NASA([1000.00, 5000.00], [ 3.69757800E+00, 6.13519700E-04, -1.25884200E-07, 1.77528100E-11, -1.13643500E-15, -1.23393000E+03, 3.18916600E+00])), transport=gas_transport(geom='linear', diam=3.458, well_depth=107.4, polar=1.6, rot_relax=3.8), note='121386') species(name='OH', atoms='O:1 H:1', thermo=(NASA([200.00, 1000.00], [ 3.99198424E+00, -2.40106655E-03, 4.61664033E-06, -3.87916306E-09, 1.36319502E-12, 3.36889836E+03, -1.03998477E-01]), NASA([1000.00, 6000.00], [ 2.83853033E+00, 1.10741289E-03, -2.94000209E-07, 4.20698729E-11, -2.42289890E-15, 3.69780808E+03, 5.84494652E+00])), transport=gas_transport(geom='linear', diam=2.75, well_depth=80.0), note='IU3/03') species(name='OH*', atoms='O:1 H:1', thermo=(NASA([300.00, 1000.00], [ 3.63726600E+00, 1.85091000E-04, -1.67616460E-06, 2.38720200E-09, -8.43144200E-13, 5.00213000E+04, 1.35886050E+00]), NASA([1000.00, 5000.00], [ 2.88273000E+00, 1.01397430E-03, -2.27687700E-07, 2.17468300E-11, -5.12630500E-16, 5.02650000E+04, 5.59571200E+00])), transport=gas_transport(geom='linear', diam=2.75, well_depth=80.0), note='121286') species(name='H2O', atoms='O:1 H:2', thermo=(NASA([300.00, 1000.00], [ 3.38684200E+00, 3.47498200E-03, -6.35469600E-06, 6.96858100E-09, -2.50658800E-12, -3.02081100E+04, 2.59023300E+00]), NASA([1000.00, 5000.00], [ 2.67214600E+00, 3.05629300E-03, -8.73026000E-07, 1.20099600E-10, -6.39161800E-15, -2.98992100E+04, 6.86281700E+00])), transport=gas_transport(geom='nonlinear', diam=2.605, well_depth=572.4, dipole=1.844, rot_relax=4.0), note='20387') species(name='N2', atoms='N:2', thermo=(NASA([300.00, 1000.00], [ 3.29867700E+00, 1.40824000E-03, -3.96322200E-06, 5.64151500E-09, -2.44485500E-12, -1.02090000E+03, 3.95037200E+00]), NASA([1000.00, 5000.00], [ 2.92664000E+00, 1.48797700E-03, -5.68476100E-07, 1.00970400E-10, -6.75335100E-15, -9.22797700E+02, 5.98052800E+00])), transport=gas_transport(geom='linear', diam=3.621, well_depth=97.53, polar=1.76, rot_relax=4.0), note='121286') species(name='HO2', atoms='O:2 H:1', thermo=(NASA([200.00, 1000.00], [ 4.30179807E+00, -4.74912097E-03, 2.11582905E-05, -2.42763914E-08, 9.29225225E-12, 2.64018485E+02, 3.71666220E+00]), NASA([1000.00, 5000.00], [ 4.17228741E+00, 1.88117627E-03, -3.46277286E-07, 1.94657549E-11, 1.76256905E-16, 3.10206839E+01, 2.95767672E+00])), transport=gas_transport(geom='nonlinear', diam=3.458, well_depth=107.4, rot_relax=1.0), note='T1/09') species(name='H2O2', atoms='O:2 H:2', thermo=(NASA([200.00, 1000.00], [ 4.31515149E+00, -8.47390622E-04, 1.76404323E-05, -2.26762944E-08, 9.08950158E-12, -1.77067437E+04, 3.27373319E+00]), NASA([1000.00, 6000.00], [ 4.57977305E+00, 4.05326003E-03, -1.29844730E-06, 1.98211400E-10, -1.13968792E-14, -1.80071775E+04, 6.64970694E-01])), transport=gas_transport(geom='nonlinear', diam=3.458, well_depth=107.4, rot_relax=3.8), note='T8/03') species(name='AR', atoms='Ar:1', thermo=(NASA([300.00, 1000.00], [ 2.50000000E+00, 0.00000000E+00, 0.00000000E+00, 0.00000000E+00, 0.00000000E+00, -7.45375000E+02, 4.36600100E+00]), NASA([1000.00, 5000.00], [ 2.50000000E+00, 0.00000000E+00, 0.00000000E+00, 0.00000000E+00, 0.00000000E+00, -7.45375000E+02, 4.36600100E+00])), transport=gas_transport(geom='atom', diam=3.33, well_depth=136.5), note='120186') species(name='CO', atoms='O:1 C:1', thermo=(NASA([300.00, 1429.00], [ 3.19036352E+00, 8.94419972E-04, -3.24927563E-08, -1.04599967E-10, 2.41965693E-14, -1.42869054E+04, 5.33277914E+00]), NASA([1429.00, 5000.00], [ 3.11216890E+00, 1.15948283E-03, -3.38480362E-07, 4.41403098E-11, -2.12862228E-15, -1.42718539E+04, 5.71725177E+00])), transport=gas_transport(geom='linear', diam=3.65, well_depth=98.1, polar=1.95, rot_relax=1.8), note='29/11/04') species(name='CO2', atoms='O:2 C:1', thermo=(NASA([300.00, 1380.00], [ 2.57930490E+00, 8.24684987E-03, -6.42716047E-06, 2.54637024E-09, -4.12030443E-13, -4.84162830E+04, 8.81141041E+00]), NASA([1380.00, 5000.00], [ 5.18953018E+00, 2.06006476E-03, -7.33575324E-07, 1.17004374E-10, -6.91729215E-15, -4.93178953E+04, -5.18289303E+00])), transport=gas_transport(geom='linear', diam=3.763, well_depth=244.0, polar=2.65, rot_relax=2.1), note='29/11/04') species(name='HE', atoms='He:1', thermo=(NASA([300.00, 1000.00], [ 2.50000000E+00, 0.00000000E+00, 0.00000000E+00, 0.00000000E+00, 0.00000000E+00, -7.45375000E+02, 9.15348800E-01]), NASA([1000.00, 5000.00], [ 2.50000000E+00, 0.00000000E+00, 0.00000000E+00, 0.00000000E+00, 0.00000000E+00, -7.45375000E+02, 9.15348900E-01])), transport=gas_transport(geom='atom', diam=2.576, well_depth=10.2), note='120186') species(name='HCO', atoms='O:1 H:1 C:1', thermo=(NASA([300.00, 1690.00], [ 3.81049965E+00, 8.13269825E-04, 3.13164701E-06, -2.39478268E-09, 5.06894554E-13, 4.03859901E+03, 4.94843165E+00]), NASA([1690.00, 5000.00], [ 3.44148164E+00, 3.52157719E-03, -1.24136118E-06, 1.97328644E-10, -1.16538616E-14, 3.97409684E+03, 6.24593456E+00])), transport=gas_transport(geom='nonlinear', diam=3.59, well_depth=498.0), note='29/11/04') #------------------------------------------------------------------------------- # Reaction data #------------------------------------------------------------------------------- # REF:HONG ET AL., PROC. COMBUST.INST. 33(1) (2011) 309316. # Reaction 1 reaction('H + O2 <=> O + OH', [1.040000e+14, 0.0, 15286.0]) # REF:SUTHERLAND ET AL., 21ST SYMPOSIUM, P. 929 (1986) # Reaction 2 reaction('O + H2 <=> H + OH', [5.080000e+04, 2.67, 6292.0]) # REF:LAM ET AL. (STANFORD) SUBMITTED TO IJCK (2012) # Reaction 3 reaction('OH + H2 <=> H + H2O', [4.380000e+13, 0.0, 6990.0]) # REF:SUTHERLAND ET AL., 23RD SYMPOSIUM, P. 51 (1990) # Reaction 4 reaction('O + H2O <=> OH + OH', [2.970000e+06, 2.02, 13400.0]) # REF:TSANG AND HAMPSON, J. PHYS. CHEM. REF. DATA, 15:1087 (1986) # Reaction 5 three_body_reaction('H2 + M <=> H + H + M', [4.577000e+19, -1.4, 104400.0], efficiencies='CO:1.9 H2O:12.0 HE:0.83 H2:2.5 CO2:3.8') # Reaction 6 three_body_reaction('O + O + M <=> O2 + M', [6.165000e+15, -0.5, 0.0], efficiencies='CO:1.9 H2:2.5 CO2:3.8 H2O:12.0 HE:0.83 AR:0.83') # Reaction 7 three_body_reaction('O + H + M <=> OH + M', [4.714000e+18, -1.0, 0.0], efficiencies='CO:1.5 H2:2.5 CO2:2.0 H2O:12.0 HE:0.75 AR:0.75') # REF: LI INT. J. CHEM. KINET. 36(10) (2004) 566575. # Reaction 8 three_body_reaction('H + OH + M <=> H2O + M', [3.500000e+22, -2.0, 0.0], efficiencies='H2:0.73 H2O:3.65 AR:0.38') # --------------- H+O2(+M) = HO2 (+M)------------------------------------- # REF: FERNANDES ET AL.,PHYS. CHEM. CHEM. PHYS. 10(29) (2008) 43134321 # Reaction 9 falloff_reaction('H + O2 (+ M) <=> HO2 (+ M)', kf=[4.650000e+12, 0.44, 0.0], kf0=[1.737000e+19, -1.23, 0.0], efficiencies='CO:1.9 H2O:10.0 CO2:3.8 H2:1.3 HE:0.0 AR:0.0', falloff=Troe(A=0.67, T3=1e-30, T1=1e+30, T2=1e+30)) # Reaction 10 falloff_reaction('H + O2 (+ HE) <=> HO2 (+ HE)', kf=[4.650000e+12, 0.44, 0.0], kf0=[9.192000e+18, -1.2, 0.0], falloff=Troe(A=0.59, T3=1e-30, T1=1e+30, T2=1e+30)) # FERNANDES X 1.5 # Reaction 11 falloff_reaction('H + O2 (+ AR) <=> HO2 (+ AR)', kf=[4.650000e+12, 0.44, 0.0], kf0=[6.810000e+18, -1.2, 0.0], falloff=Troe(A=0.7, T3=1e-30, T1=1e+30, T2=1e+30)) # REF: BATES ET AL. PHYS. CHEM. CHEM. PHYS. 3(12) (2001) 23372342. # ---------------------------------------------------------------------------- # REF MUELLER ET AL., INT. J. CHEM. KINET. 31(10) (1999) 705724. # Reaction 12 reaction('HO2 + H <=> OH + OH', [7.079000e+13, 0.0, 295.0]) # REF: MICHAEL ET AL., PROC. COMBUST. INST. 28(2) (2000) 14711478. # Reaction 13 reaction('H2 + O2 <=> H + HO2', [5.176000e+05, 2.433, 53502.0]) # REF:BAULCH ET AL., J. PHYS. CHEM. REF DATA, 21(3) (1992) 411-734 # Reaction 14 reaction('HO2 + O <=> OH + O2', [3.250000e+13, 0.0, 0.0]) # REF:KEYSER, J. PHYS. CHEM. 92 (1988) 11931200. REDUCED BY 15% # Reaction 15 reaction('HO2 + OH <=> H2O + O2', [2.456000e+13, 0.0, -497.0]) # REF:HIPPLER ET AL., J. CHEM. PHYS. 93(3) (1990) 17551760. # Reaction 16 reaction('HO2 + HO2 <=> O2 + H2O2', [1.300000e+11, 0.0, -1630.0], options='duplicate') # Reaction 17 reaction('HO2 + HO2 <=> O2 + H2O2', [3.658000e+14, 0.0, 12000.0], options='duplicate') # HIPPLER X 0.87 # --------------------- H2O2(+M) = OH+OH(+M)----------------------------------------------------- # REF: TROE, COMBUST. FLAME 158(4) (2011) 594601. # Reaction 18 falloff_reaction('H2O2 (+ M) <=> OH + OH (+ M)', kf=[2.000000e+12, 0.9, 48749.0], kf0=[2.490000e+24, -2.3, 48749.0], efficiencies='CO:2.8 HE:0.65 N2:1.5 O2:1.2 H2:3.7 CO2:1.6 H2O2:7.7 H2O:0.0', falloff=Troe(A=0.43, T3=1e-30, T1=1e+30)) # DEFINED IN ARGON # EFFICIENCIES FOR H2 AND CO TAKEN FROM LI ET AL., INT. J. CHEM. KINET. 36:566-575 (2004) # Reaction 19 falloff_reaction('H2O2 (+ H2O) <=> OH + OH (+ H2O)', kf=[2.000000e+12, 0.9, 48749.0], kf0=[1.865000e+25, -2.3, 48749.0], falloff=Troe(A=0.51, T3=1e-30, T1=1e+30)) # --------------------------------------------------------------------------------------------- # REF:TSANG AND HAMPSON, J. PHYS. CHEM. REF. DATA 15 (1986) 10871280. # Reaction 20 reaction('H2O2 + H <=> H2O + OH', [2.410000e+13, 0.0, 3970.0]) # REF: ELLINGSON ET AL., J. PHYS. CHEM. A 111(51) (2007) 1355413566. (FIT TO THE THEORETICAL RATE) # Reaction 21 reaction('H2O2 + H <=> H2 + HO2', [2.150000e+10, 1.0, 6000.0]) # REF:TSANG AND HAMPSON, J. PHYS. CHEM. REF. DATA 15 (1986) 10871280. # Reaction 22 reaction('H2O2 + O <=> OH + HO2', [9.550000e+06, 2.0, 3970.0]) # REF: HONG ET AL., J. PHYS. CHEM. A 114(18) (2010) 57185727. # Reaction 23 reaction('H2O2 + OH <=> H2O + HO2', [1.740000e+12, 0.0, 318.0], options='duplicate') # Reaction 24 reaction('H2O2 + OH <=> H2O + HO2', [7.590000e+13, 0.0, 7269.0], options='duplicate') # --------------------------------------------------------------------------------------------- # -------------END OF H2 MECHANISM------------------------------------------------------------- # --------------------------------------------------------------------------------------------- # REF: TROE, J. PHYS. CHEM. 83 (1979) 114126. X 0.76 # Reaction 25 falloff_reaction('CO + O (+ M) <=> CO2 (+ M)', kf=[1.362000e+10, 0.0, 2384.0], kf0=[1.173000e+24, -2.79, 4191.0], efficiencies='CO:1.75 H2:2.0 CO2:3.6 H2O:12.0 HE:0.7 AR:0.7') # REF: WESTMORELAND ET AL, AICHE JOURNAL 32(12) (1986) 19711979. X 0.87 # REF:TSANG AND HAMPSON, J. PHYS. CHEM. REF. DATA 15 (1986) 10871280. # Reaction 26 reaction('CO + O2 <=> CO2 + O', [1.119000e+12, 0.0, 47700.0]) # REF: JOSHI AND WANG, INT. J. CHEM. KINET. 38(1) (2006) 5773. # Reaction 27 reaction('CO + OH <=> CO2 + H', [7.015000e+04, 2.053, -355.67], options='duplicate') # Reaction 28 reaction('CO + OH <=> CO2 + H', [5.757000e+12, -0.664, 331.83], options='duplicate') # REF: YOU ET AL. J. PHYS. CHEM. A 111(19) (2007) 40314042. # Reaction 29 reaction('CO + HO2 <=> CO2 + OH', [1.570000e+05, 2.18, 17940.0]) # REF: LI ET AL. INT. J. CHEM. KINET. 39(3) (2007) 109136. # Reaction 30 three_body_reaction('HCO + M <=> H + CO + M', [4.750000e+11, 0.66, 14870.0], efficiencies='CO:1.5 H2:2.0 H2O:12.0 CO2:2.0') # REF: TIMONEN ET AL., J. PHYS. CHEM. 92(3) (1988) 651655. # Reaction 31 reaction('HCO + O2 <=> CO + HO2', [7.580000e+12, 0.0, 410.0]) # REF: TIMONEN ET AL., J. PHYS. CHEM. 91(3) (1987) 692694. # Reaction 32 reaction('HCO + H <=> CO + H2', [7.340000e+13, 0.0, 0.0]) # REF:TSANG AND HAMPSON, J. PHYS. CHEM. REF. DATA 15 (1986) 10871280. # Reaction 33 reaction('HCO + O <=> CO + OH', [3.020000e+13, 0.0, 0.0]) # Reaction 34 reaction('HCO + O <=> CO2 + H', [3.000000e+13, 0.0, 0.0]) # REF: BAULCH ET AL., J. PHYS. CHEM. REF. DATA 21(3) (1992) 411734. # Reaction 35 reaction('HCO + OH <=> CO + H2O', [1.020000e+14, 0.0, 0.0]) # REF:TSANG AND HAMPSON, J. PHYS. CHEM. REF. DATA 15 (1986) 10871280. # Reaction 36 reaction('HCO + HO2 => CO2 + H + OH', [3.000000e+13, 0.0, 0.0]) # Reaction 37 reaction('HCO + HCO => H2 + CO + CO', [3.000000e+12, 0.0, 0.0]) # --------------------------------------------------------------------------------------------- # -------------END OF H2/CO MECHANISM---------------------------------------------------------- # --------------------------------------------------------------------------------------------- # -------------------------------OH* MECHANISM------------------------------------------------- # REF: KATHROTIA ET AL., COMBUST. FLAME 157(7) (2010) 12611273 # Reaction 38 three_body_reaction('H + O + M <=> OH* + M', [1.500000e+13, 0.0, 5975.0], efficiencies='H2:1.0 O2:0.4 H2O:6.5 N2:0.4 AR:0.35') # REF: TAMURA ET AL., COMBUST. FLAME 114(3-4) (1998) 502514. # Reaction 39 reaction('OH* + H2O <=> OH + H2O', [5.930000e+12, 0.5, -860.0]) # Reaction 40 reaction('OH* + H2 <=> OH + H2', [2.950000e+12, 0.5, -444.0]) # Reaction 41 reaction('OH* + N2 <=> OH + N2', [1.080000e+11, 0.5, -1242.0]) # Reaction 42 reaction('OH* + OH <=> OH + OH', [6.010000e+12, 0.5, -764.0]) # Reaction 43 reaction('OH* + H <=> OH + H', [1.310000e+12, 0.5, -167.0]) # Reaction 44 reaction('OH* + O2 <=> OH + O2', [2.100000e+12, 0.5, -478.0]) # Reaction 45 reaction('OH* + CO2 <=> OH + CO2', [2.750000e+12, 0.5, -968.0]) # Reaction 46 reaction('OH* + CO <=> OH + CO', [3.230000e+12, 0.5, -787.0]) # REF: PAUL ET AL., J. CHEM. PHYS. 102(21) (1995) 83788384. # Reaction 47 reaction('OH* + AR <=> OH + AR', [1.690000e+12, 0.0, 4135.0]) # REF: SMITH ET AL., COMBUST. FLAME 131(1-2) (2002) 5969. # Reaction 48 reaction('OH* => OH', [1.450000e+06, 0.0, 0.0]) # ----------------------------END OH* MECHANISM-------------------------------------------------