""" ------------------------------------------------------------------------------- H2-O2-N2 reaction mechanism (includes NO and OH* formation) This mechanism is used for the simulations in: J. Melguizo-Gavilanes, L.R. Boeck, R. Mevel, J.E. Shepherd. Hot surface ignition of stoichiometric hydrogen-air mixtures. International Journal of Hydrogen Energy, 42(11):7393-7403, 2017. doi:10.1016/j.ijhydene.2016.05.095. J. Melguizo-Gavilanes, S. Coronel, R. Mevel, and J. E. Shepherd. Dynamics of ignition of stoichiometric hydrogen-air mixtures by moving heated particles. International Journal of Hydrogen Energy, 42(11):7380-7392, 2017. doi:10.1016/j.ijhydene.2016.05.206 The rates are abstracted from the mechanism described in: R. Mevel and S. Javoy and F. Lafosse and N. Chaumeix and G. Dupr\'e and Paillard, C. -E., Hydrogen-nitrous oxide delay time: shock tube experimental study and kinetic modelling, Proceedings of The Combustion Institute, 2009, volume 32,359-366. doi:10.1016/j.proci.2008.06.171 ------------------------------------------------------------------------------- """ units(length='cm', time='s', quantity='mol', act_energy='cal/mol') ideal_gas(name='gas', elements="H O N Ar He", species="""H O H2 O2 OH H2O N2 N NO HO2 H2O2 AR OH* HE""", 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='O', atoms='O:1', thermo=(NASA([200.00, 1000.00], [ 3.16826710E+00, -3.27931884E-03, 6.64306396E-06, -6.12806624E-09, 2.11265971E-12, 2.91222592E+04, 2.05193346E+00]), NASA([1000.00, 6000.00], [ 2.54363697E+00, -2.73162486E-05, -4.19029520E-09, 4.95481845E-12, -4.79553694E-16, 2.92260120E+04, 4.92229457E+00])), transport=gas_transport(geom='atom', diam=2.75, well_depth=80.0), note='L1/90') species(name='H2', atoms='H:2', thermo=(NASA([200.00, 1000.00], [ 2.34430290E+00, 7.98042480E-03, -1.94779170E-05, 2.01569670E-08, -7.37602890E-12, -9.17924130E+02, 6.83002180E-01]), NASA([1000.00, 6000.00], [ 2.93283050E+00, 8.26598020E-04, -1.46400570E-07, 1.54098510E-11, -6.88796150E-16, -8.13055820E+02, -1.02431640E+00])), transport=gas_transport(geom='linear', diam=2.92, well_depth=38.0, polar=0.79, rot_relax=280.0), note='RUS78') species(name='O2', atoms='O:2', thermo=(NASA([200.00, 1000.00], [ 3.78245636E+00, -2.99673415E-03, 9.84730200E-06, -9.68129508E-09, 3.24372836E-12, -1.06394356E+03, 3.65767573E+00]), NASA([1000.00, 6000.00], [ 3.66096083E+00, 6.56365523E-04, -1.41149485E-07, 2.05797658E-11, -1.29913248E-15, -1.21597725E+03, 3.41536184E+00])), transport=gas_transport(geom='linear', diam=3.458, well_depth=107.4, polar=1.6, rot_relax=3.8), note='RUS89') 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='H2O', atoms='O:1 H:2', thermo=(NASA([200.00, 1000.00], [ 4.19863520E+00, -2.03640170E-03, 6.52034160E-06, -5.48792690E-09, 1.77196800E-12, -3.02937260E+04, -8.49009010E-01]), NASA([1000.00, 6000.00], [ 2.67703890E+00, 2.97318160E-03, -7.73768890E-07, 9.44335140E-11, -4.26899910E-15, -2.98858940E+04, 6.88255000E+00])), transport=gas_transport(geom='nonlinear', diam=2.605, well_depth=572.4, dipole=1.844, rot_relax=4.0), note='L5/89') species(name='N2', atoms='N:2', thermo=(NASA([200.00, 1000.00], [ 3.53100528E+00, -1.23660988E-04, -5.02999433E-07, 2.43530612E-09, -1.40881235E-12, -1.04697628E+03, 2.96747038E+00]), NASA([1000.00, 6000.00], [ 2.95257637E+00, 1.39690040E-03, -4.92631603E-07, 7.86010195E-11, -4.60755204E-15, -9.23948688E+02, 5.87188762E+00])), transport=gas_transport(geom='linear', diam=3.621, well_depth=97.53, polar=1.76, rot_relax=4.0), note='G8/02') species(name='N', atoms='N:1', thermo=(NASA([200.00, 1000.00], [ 2.50000000E+00, 0.00000000E+00, 0.00000000E+00, 0.00000000E+00, 0.00000000E+00, 5.61046370E+04, 4.19390870E+00]), NASA([1000.00, 6000.00], [ 2.41594290E+00, 1.74890650E-04, -1.19023690E-07, 3.02262450E-11, -2.03609820E-15, 5.61337730E+04, 4.64960960E+00])), transport=gas_transport(geom='atom', diam=3.298, well_depth=71.4), note='L6/88') species(name='NO', atoms='O:1 N:1', thermo=(NASA([200.00, 1000.00], [ 4.21847630E+00, -4.63897600E-03, 1.10410220E-05, -9.33613540E-09, 2.80357700E-12, 9.84462300E+03, 2.28084640E+00]), NASA([1000.00, 6000.00], [ 3.26060560E+00, 1.19110430E-03, -4.29170480E-07, 6.94576690E-11, -4.03360990E-15, 9.92097460E+03, 6.36930270E+00])), transport=gas_transport(geom='linear', diam=3.621, well_depth=97.53, polar=1.76, rot_relax=4.0), note='RUS78') species(name='HO2', atoms='O:2 H:1', thermo=(NASA([200.00, 1000.00], [ 4.30178800E+00, -4.74902010E-03, 2.11579530E-05, -2.42759610E-08, 9.29206700E-12, 2.94808760E+02, 3.71670100E+00]), NASA([1000.00, 6000.00], [ 4.17226590E+00, 1.88120980E-03, -3.46292970E-07, 1.94685160E-11, 1.76091530E-16, 6.18188510E+01, 2.95779740E+00])), transport=gas_transport(geom='nonlinear', diam=3.458, well_depth=107.4, rot_relax=1.0), note='L5/89') 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([200.00, 1000.00], [ 2.50000000E+00, 0.00000000E+00, 0.00000000E+00, 0.00000000E+00, 0.00000000E+00, -7.45375000E+02, 4.37967490E+00]), NASA([1000.00, 6000.00], [ 2.50000000E+00, 0.00000000E+00, 0.00000000E+00, 0.00000000E+00, 0.00000000E+00, -7.45375000E+02, 4.37967490E+00])), transport=gas_transport(geom='atom', diam=3.33, well_depth=136.5), note='L6/88') species(name='OH*', atoms='O:1 H:1', thermo=(NASA([200.00, 1500.00], [ 3.66109869E+00, -9.79456212E-04, 1.78354820E-06, -7.68428401E-10, 1.00625336E-13, 5.04491534E+04, 8.95237048E-01]), NASA([1500.00, 6000.00], [ 2.82384689E+00, 1.26941983E-03, -3.30833058E-07, 4.47202686E-11, -2.69934189E-15, 5.06815075E+04, 5.23958687E+00])), transport=gas_transport(geom='linear', diam=2.75, well_depth=80.0), note='SDT18') species(name='HE', atoms='He:1', thermo=(NASA([200.00, 1000.00], [ 2.50000000E+00, 0.00000000E+00, 0.00000000E+00, 0.00000000E+00, 0.00000000E+00, -7.45375000E+02, 9.28723974E-01]), NASA([1000.00, 6000.00], [ 2.50000000E+00, 0.00000000E+00, 0.00000000E+00, 0.00000000E+00, 0.00000000E+00, -7.45375000E+02, 9.28723974E-01])), transport=gas_transport(geom='atom', diam=2.576, well_depth=10.2), note='L10/90') #------------------------------------------------------------------------------- # Reaction data #------------------------------------------------------------------------------- # H2 REACTIONS # Reaction 1 three_body_reaction('H2 + M <=> H + H + M', [4.570000e+19, -1.4, 104380.0], efficiencies='H2:2.5 AR:0.0 H2O:12.0',options=["duplicate"]) # 1 Tsang & Hampson,J.Phys.Chem.Ref.Data,15,1986. # Reaction 2 reaction('H2 + AR <=> H + H + AR', [5.840000e+18, -1.1, 104380.0]) # 2 Tsang & Hampson,J.Phys.Chem.Ref.Data,15,1986. # Reaction 3 reaction('H2 + O2 <=> OH + OH', [2.500000e+12, 0.0, 39000.0]) # 3 Konnov # Reaction 4 reaction('H + H + H <=> H2 + H', [3.200000e+15, 0.0, 0.0],options=["duplicate"]) # 4 Konnov # Reaction 5 reaction('H + HO2 <=> H2O + O', [3.000000e+13, 0.0, 1720.0]) # 5 Konnov # O REACTIONS # Reaction 6 reaction('O + H2 <=> H + OH', [5.080000e+04, 2.67, 6290.0]) # 6 Sutherland et. al., 21st Symp. on Comb.,p929,1986. # Reaction 7 three_body_reaction('O + O + M <=> O2 + M', [6.160000e+15, -0.5, 0.0], efficiencies='H2:2.5 AR:0.0 H2O:12.0') # 7 Tsang & Hampson,J.Phys.Chem.Ref.Data,15,1986. # Reaction 8 reaction('O + O + AR <=> O2 + AR', [1.890000e+13, 0.0, -1788.0]) # 8 Tsang & Hampson,J.Phys.Chem.Ref.Data,15,1986. # H REACTIONS # Reaction 9 reaction('H + O2 <=> O + OH', [1.910000e+14, 0.0, 16439.0]) # 9 Pirraglia et. al. (TJK)### # Reaction 10 falloff_reaction('H + O2 (+ M) <=> HO2 (+ M)', kf=[1.480000e+12, 0.6, 0.0], kf0=[3.482000e+16, -0.411, -1115.0], efficiencies='H2:2.5 AR:0.0 H2O:12.0', falloff=Troe(A=0.5, T3=1e-30, T1=1e+30)) # 10 Mueller et al Proc. Comb. Ins. 27, (1998) # Reaction 11 falloff_reaction('H + O2 (+ AR) <=> HO2 (+ AR)', kf=[1.480000e+13, 0.6, 0.0], kf0=[1.490000e+15, 0.0, -1000.0], falloff=Troe(A=0.45, T3=1e-30, T1=1e+30)) # 11 TJK baseline recommendation Should this be x 10^12 or 10 ^13? # Reaction 12 three_body_reaction('H + O + M <=> OH + M', [4.710000e+18, -1.0, 0.0], efficiencies='H2:2.5 AR:0.75 H2O:12.0') # 12 Tsang & Hampson,J.Phys.Chem.Ref.Data,15,1986 # OH REACTIONS # Reaction 13 reaction('OH + H2 <=> H2O + H', [2.160000e+08, 1.51, 3430.0]) # 13 Michael & Sutherland,J.Phys.Chem.,92,3853,1988 # Reaction 14 reaction('H2O + O <=> OH + OH', [2.970000e+06, 2.02, 13400.0]) # 14 Sutherland et. al. Proc Comb. Ins., 28 51 (1990) # Reaction 15 falloff_reaction('H2O2 (+ M) <=> OH + OH (+ M)', kf=[2.950000e+14, 0.0, 48430.0], kf0=[1.200000e+17, 0.0, 45500.0], efficiencies='H2:2.5 AR:0.0 H2O:12.0', falloff=Troe(A=0.5, T3=1e-90, T1=1e+90)) # 15 Brouwer,Cobos,Troe,Duba,&Crim,J.Chem.Phys.86,6171,1987. # Reaction 16 falloff_reaction('H2O2 (+ AR) <=> OH + OH (+ AR)', kf=[2.950000e+14, 0.0, 48430.0], kf0=[1.900000e+16, 0.0, 43000.0], falloff=Troe(A=0.5, T3=1e-29, T1=1e+31)) # 16 Brouwer,Cobos,Troe,Duba,&Crim,J.Chem.Phys.86,6171,1987. # Reaction 17 three_body_reaction('OH + H + M <=> H2O + M', [2.210000e+22, -2.0, 0.0], efficiencies='H2:2.5 AR:0.0 H2O:12.0') # 17 Tsang & Hampson,J.Phys.Chem.Ref.Data,15,1986 # Reaction 18 reaction('OH + H + AR <=> H2O + AR', [8.410000e+21, -2.0, 0.0]) # 18 Tsang & Hampson,J.Phys.Chem.Ref.Data,15,1986 # HO2 REACTIONS # Reaction 19 reaction('HO2 + O <=> O2 + OH', [3.300000e+13, 0.0, 0.0]) # 19 Baulch et al., JPC Ref Data, 21:411 (1992) # Reaction 20 reaction('HO2 + H <=> H2 + O2', [1.660000e+13, 0.0, 823.0]) # 20 Mueller et al. IJCK 31, 113 (1995) # Reaction 21 reaction('HO2 + H <=> OH + OH', [7.080000e+13, 0.0, 295.0]) # 21 Mueller et al. IJCK 31, 113 (1995) # Reaction 22 reaction('HO2 + OH <=> H2O + O2', [2.890000e+13, 0.0, -497.0]) # 22 Keyser,L.F., J.Phys.Chem.92,1193,1988 # Reaction 23 reaction('HO2 + HO2 <=> H2O2 + O2', [4.200000e+14, 0.0, 11982.0], options='duplicate') # 23 Hippler,Troe,Willner,J.Chem.Phys.93,1755,1990 # Reaction 24 reaction('HO2 + HO2 <=> H2O2 + O2', [1.300000e+11, 0.0, -1629.0], options='duplicate') # 24 Hippler,Troe,Willner,J.Chem.Phys.93,1755,1990 # H2O2 REACTIONS # Reaction 25 reaction('H2O2 + O <=> OH + HO2', [9.550000e+06, 2.0, 3970.0]) # 25 Tsang & Hampson,J.Phys.Chem.Ref.Data,15,1986 # Reaction 26 reaction('H2O2 + H <=> H2O + OH', [2.400000e+13, 0.0, 3970.0]) # 26 Tsang and Hampson, JPC Ref. Data, 15:1087 (1986) # Reaction 27 reaction('H2O2 + H <=> HO2 + H2', [4.820000e+13, 0.0, 7950.0]) # 27 Tsang & Hampson,J.Phys.Chem.Ref.Data,15,1986 # Reaction 28 reaction('H2O2 + OH <=> H2O + HO2', [1.000000e+12, 0.0, 0.0], options='duplicate') # 28 Hippler et. al. Double Exponential fit by(TJK) # Reaction 29 reaction('H2O2 + OH <=> H2O + HO2', [5.800000e+14, 0.0, 9557.0], options='duplicate') # 29 Hippler et. al. Double Exponential fit by(TJK)### # ***************************************************************** # ******************Ractions radicaux OHexcit******************** # ***************************************************************** # Reaction 30 three_body_reaction('H + O + M <=> OH* + M', [6.000000e+14, 0.0, 6940.0]) # 31 Petersen 1 AIAA Paper, n 2004-4164, 10 p. # Reaction 31 reaction('OH* + AR <=> OH + AR', [2.170000e+10, 0.5, 2060.0]) # 32 Paul et al. # Reaction 32 reaction('OH* + H2O <=> OH + H2O', [5.920000e+12, 0.5, -861.0]) # 33 Tamura et al. # Reaction 33 reaction('OH* + H <=> OH + H', [1.500000e+12, 0.5, 0.0]) # 34 Hidaka Bull. Chem. Soc. Jpn., 58,p 2911. # Reaction 34 reaction('OH* + H2 <=> OH + H2', [2.950000e+12, 0.5, -444.0]) # 35 Tamura et al. # Reaction 35 reaction('OH* + O2 <=> OH + O2', [2.100000e+12, 0.5, -482.0]) # 36 Tamura et al. # Reaction 36 reaction('OH* + O <=> OH + O', [1.500000e+12, 0.5, 0.0]) # 37 Hidaka Bull. Chem. Soc. Jpn., 58,p 2911. # Reaction 37 reaction('OH* + OH <=> OH + OH', [1.500000e+12, 0.5, 0.0]) # 38 Hidaka Bull. Chem. Soc. Jpn., 58,p 2911. # Reaction 38 reaction('OH* <=> OH', [1.400000e+06, 0.0, 0.0]) # 39 Hidaka Bull. Chem. Soc. Jpn., 58,p 2911. # NO REACTIONS # Reaction 39 reaction('N2 + O <=> NO + N', [1.800000e+14, 0.0, 76100.0]) # 40 Konnov # Reaction 40 reaction('N + O2 <=> NO + O', [9.000000e+09, 1.0, 6500.0]) # 41 Konnov # Reaction 41 three_body_reaction('NO + M <=> N + O + M', [9.640000e+14, 0.0, 148300.0], efficiencies='NO:3.0 N2:1.5') # 42 Konnov # Reaction 42 reaction('NO + NO <=> N2 + O2', [3.000000e+11, 0.0, 65000.0]) # 43 Konnov