""" ------------------------------------------------------------------------------- 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=(NASA9([200.00, 1000.00], [ 0.000000000E+00, 0.000000000E+00, 2.500000000E+00, 0.000000000E+00, 0.000000000E+00, 0.000000000E+00, 0.000000000E+00, 2.547370801E+04, -4.466828530E-01]), NASA9([1000.00, 6000.00], [ 6.078774250E+01, -1.819354417E-01, 2.500211817E+00, -1.226512864E-07, 3.732876330E-11, -5.687744560E-15, 3.410210197E-19, 2.547486398E+04, -4.481917770E-01]), NASA9([6000.00, 20000.00], [ 2.173757694E+08, -1.312035403E+05, 3.399174200E+01, -3.813999680E-03, 2.432854837E-07, -7.694275540E-12, 9.644105630E-17, 1.067638086E+06, -2.742301051E+02])), transport=gas_transport(geom='atom', diam=2.05, well_depth=145.0), note='D0(H2):Herzberg,1970. Moore,1972. Gordon,1999. [g 6/97]') species(name='O', atoms='O:1', thermo=(NASA9([200.00, 1000.00], [-7.953611300E+03, 1.607177787E+02, 1.966226438E+00, 1.013670310E-03, -1.110415423E-06, 6.517507500E-10, -1.584779251E-13, 2.840362437E+04, 8.404241820E+00]), NASA9([1000.00, 6000.00], [ 2.619020262E+05, -7.298722030E+02, 3.317177270E+00, -4.281334360E-04, 1.036104594E-07, -9.438304330E-12, 2.725038297E-16, 3.392428060E+04, -6.679585350E-01]), NASA9([6000.00, 20000.00], [ 1.779004264E+08, -1.082328257E+05, 2.810778365E+01, -2.975232262E-03, 1.854997534E-07, -5.796231540E-12, 7.191720164E-17, 8.890942630E+05, -2.181728151E+02])), transport=gas_transport(geom='atom', diam=2.75, well_depth=80.0), note='D0(O2):Brix,1954. Moore,1976. Gordon,1999. [g 5/97]') species(name='H2', atoms='H:2', thermo=(NASA9([200.00, 1000.00], [ 4.078323210E+04, -8.009186040E+02, 8.214702010E+00, -1.269714457E-02, 1.753605076E-05, -1.202860270E-08, 3.368093490E-12, 2.682484665E+03, -3.043788844E+01]), NASA9([1000.00, 6000.00], [ 5.608128010E+05, -8.371504740E+02, 2.975364532E+00, 1.252249124E-03, -3.740716190E-07, 5.936625200E-11, -3.606994100E-15, 5.339824410E+03, -2.202774769E+00]), NASA9([6000.00, 20000.00], [ 4.966884120E+08, -3.147547149E+05, 7.984121880E+01, -8.414789210E-03, 4.753248350E-07, -1.371873492E-11, 1.605461756E-16, 2.488433516E+06, -6.695728110E+02])), transport=gas_transport(geom='linear', diam=2.92, well_depth=38.0, polar=0.79, rot_relax=280.0), note='Ref-Elm. Gurvich,1978 pt1 p103 pt2 p31. [tpis78]') species(name='O2', atoms='O:2', thermo=(NASA9([200.00, 1000.00], [-3.425563420E+04, 4.847000970E+02, 1.119010961E+00, 4.293889240E-03, -6.836300520E-07, -2.023372700E-09, 1.039040018E-12, -3.391454870E+03, 1.849699470E+01]), NASA9([1000.00, 6000.00], [-1.037939022E+06, 2.344830282E+03, 1.819732036E+00, 1.267847582E-03, -2.188067988E-07, 2.053719572E-11, -8.193467050E-16, -1.689010929E+04, 1.738716506E+01]), NASA9([6000.00, 20000.00], [ 4.975294300E+08, -2.866106874E+05, 6.690352250E+01, -6.169959020E-03, 3.016396027E-07, -7.421416600E-12, 7.278175770E-17, 2.293554027E+06, -5.530621610E+02])), transport=gas_transport(geom='linear', diam=3.458, well_depth=107.4, polar=1.6, rot_relax=3.8), note='Ref-Elm. Gurvich,1989 pt1 p94 pt2 p9. [tpis89]') species(name='OH', atoms='O:1 H:1', thermo=(NASA9([200.00, 1500.00], [ 0.000000000E+00, 0.000000000E+00, 3.564596310E+00, -3.112199510E-04, 3.374757480E-07, 2.088993400E-10, -1.180595260E-13, 3.433870050E+03, 1.904582800E+00]), NASA9([1500.00, 6000.00], [ 0.000000000E+00, 0.000000000E+00, 2.637976260E+00, 1.367458500E-03, -4.077165390E-07, 6.244817160E-11, -3.578990740E-15, 3.785113130E+03, 7.021351220E+00])), transport=gas_transport(geom='linear', diam=2.75, well_depth=80.0), note='Partition fit by JES 14-Jul-2018 12:50:05') species(name='H2O', atoms='O:1 H:2', thermo=(NASA9([200.00, 1000.00], [-3.947960830E+04, 5.755731020E+02, 9.317826530E-01, 7.222712860E-03, -7.342557370E-06, 4.955043490E-09, -1.336933246E-12, -3.303974310E+04, 1.724205775E+01]), NASA9([1000.00, 6000.00], [ 1.034972096E+06, -2.412698562E+03, 4.646110780E+00, 2.291998307E-03, -6.836830480E-07, 9.426468930E-11, -4.822380530E-15, -1.384286509E+04, -7.978148510E+00])), transport=gas_transport(geom='nonlinear', diam=2.605, well_depth=572.4, dipole=1.844, rot_relax=4.0), note='Hf:Cox,1989. Woolley,1987. TRC(10/88) tuv25. [g 8/89]') species(name='N2', atoms='N:2', thermo=(NASA9([200.00, 1000.00], [ 2.210371497E+04, -3.818461820E+02, 6.082738360E+00, -8.530914410E-03, 1.384646189E-05, -9.625793620E-09, 2.519705809E-12, 7.108460860E+02, -1.076003744E+01]), NASA9([1000.00, 6000.00], [ 5.877124060E+05, -2.239249073E+03, 6.066949220E+00, -6.139685500E-04, 1.491806679E-07, -1.923105485E-11, 1.061954386E-15, 1.283210415E+04, -1.586640027E+01]), NASA9([6000.00, 20000.00], [ 8.310139160E+08, -6.420733540E+05, 2.020264635E+02, -3.065092046E-02, 2.486903333E-06, -9.705954110E-11, 1.437538881E-15, 4.938707040E+06, -1.672099740E+03])), transport=gas_transport(geom='linear', diam=3.621, well_depth=97.53, polar=1.76, rot_relax=4.0), note='Ref-Elm. Gurvich,1978 pt1 p280 pt2 p207. [tpis78]') species(name='N', atoms='N:1', thermo=(NASA9([200.00, 1000.00], [ 0.000000000E+00, 0.000000000E+00, 2.500000000E+00, 0.000000000E+00, 0.000000000E+00, 0.000000000E+00, 0.000000000E+00, 5.610463780E+04, 4.193905036E+00]), NASA9([1000.00, 6000.00], [ 8.876501380E+04, -1.071231500E+02, 2.362188287E+00, 2.916720081E-04, -1.729515100E-07, 4.012657880E-11, -2.677227571E-15, 5.697351330E+04, 4.865231506E+00]), NASA9([6000.00, 20000.00], [ 5.475181050E+08, -3.107574980E+05, 6.916782740E+01, -6.847988130E-03, 3.827572400E-07, -1.098367709E-11, 1.277986024E-16, 2.550585618E+06, -5.848769753E+02])), transport=gas_transport(geom='atom', diam=3.298, well_depth=71.4), note='Hf:Cox,1989. Moore,1975. Gordon,1999. [g 5/97]') species(name='NO', atoms='O:1 N:1', thermo=(NASA9([200.00, 1000.00], [-1.143916503E+04, 1.536467592E+02, 3.431468730E+00, -2.668592368E-03, 8.481399120E-06, -7.685111050E-09, 2.386797655E-12, 9.098214410E+03, 6.728725490E+00]), NASA9([1000.00, 6000.00], [ 2.239018716E+05, -1.289651623E+03, 5.433936030E+00, -3.656034900E-04, 9.880966450E-08, -1.416076856E-11, 9.380184620E-16, 1.750317656E+04, -8.501669090E+00]), NASA9([6000.00, 20000.00], [-9.575303540E+08, 5.912434480E+05, -1.384566826E+02, 1.694339403E-02, -1.007351096E-06, 2.912584076E-11, -3.295109350E-16, -4.677501240E+06, 1.242081216E+03])), transport=gas_transport(geom='linear', diam=3.621, well_depth=97.53, polar=1.76, rot_relax=4.0), note='Gurvich,1978,1989 pt1 p326 pt2 p203. [tpis89]') species(name='HO2', atoms='O:2 H:1', thermo=(NASA9([200.00, 1000.00], [-7.598882540E+04, 1.329383918E+03, -4.677388240E+00, 2.508308202E-02, -3.006551588E-05, 1.895600056E-08, -4.828567390E-12, -5.873350960E+03, 5.193602140E+01]), NASA9([1000.00, 6000.00], [-1.810669724E+06, 4.963192030E+03, -1.039498992E+00, 4.560148530E-03, -1.061859447E-06, 1.144567878E-10, -4.763064160E-15, -3.200817190E+04, 4.066850920E+01])), transport=gas_transport(geom='nonlinear', diam=3.458, well_depth=107.4, rot_relax=1.0), note='Hf:Hills,1984 & NASA data. Jacox,1998 p153. [g 4/02]') species(name='H2O2', atoms='O:2 H:2', thermo=(NASA9([200.00, 1000.00], [-9.279533580E+04, 1.564748385E+03, -5.976460140E+00, 3.270744520E-02, -3.932193260E-05, 2.509255235E-08, -6.465045290E-12, -2.494004728E+04, 5.877174180E+01]), NASA9([1000.00, 6000.00], [ 1.489428027E+06, -5.170821780E+03, 1.128204970E+01, -8.042397790E-05, -1.818383769E-08, 6.947265590E-12, -4.827831900E-16, 1.418251038E+04, -4.650855660E+01])), transport=gas_transport(geom='nonlinear', diam=3.458, well_depth=107.4, rot_relax=3.8), note='Hf:Gurvich,1989 pt1 p127. Gurvich,1978 pt1 p121. [g 6/99]') species(name='AR', atoms='Ar:1', thermo=(NASA9([200.00, 1000.00], [ 0.000000000E+00, 0.000000000E+00, 2.500000000E+00, 0.000000000E+00, 0.000000000E+00, 0.000000000E+00, 0.000000000E+00, -7.453750000E+02, 4.379674910E+00]), NASA9([1000.00, 6000.00], [ 2.010538475E+01, -5.992661070E-02, 2.500069401E+00, -3.992141160E-08, 1.205272140E-11, -1.819015576E-15, 1.078576636E-19, -7.449939610E+02, 4.379180110E+00]), NASA9([6000.00, 20000.00], [-9.951265080E+08, 6.458887260E+05, -1.675894697E+02, 2.319933363E-02, -1.721080911E-06, 6.531938460E-11, -9.740147729E-16, -5.078300340E+06, 1.465298484E+03])), transport=gas_transport(geom='atom', diam=3.33, well_depth=136.5), note='Ref-Elm. Moore,1971. Gordon,1999. [g 3/98]') species(name='OH*', atoms='O:1 H:1', thermo=(NASA9([200.00, 1500.00], [ 0.000000000E+00, 0.000000000E+00, 3.661098690E+00, -9.794562120E-04, 1.783548200E-06, -7.684284010E-10, 1.006253360E-13, 5.044915340E+04, 8.952370480E-01]), NASA9([1500.00, 6000.00], [ 0.000000000E+00, 0.000000000E+00, 2.823846890E+00, 1.269419830E-03, -3.308330580E-07, 4.472026860E-11, -2.699341890E-15, 5.068150750E+04, 5.239586870E+00])), transport=gas_transport(geom='linear', diam=2.75, well_depth=80.0), note='Partition fit by JES 14-Jul-2018 12:49:16') species(name='HE', atoms='He:1', thermo=(NASA9([200.00, 1000.00], [ 0.000000000E+00, 0.000000000E+00, 2.500000000E+00, 0.000000000E+00, 0.000000000E+00, 0.000000000E+00, 0.000000000E+00, -7.453750000E+02, 9.287239740E-01]), NASA9([1000.00, 6000.00], [ 0.000000000E+00, 0.000000000E+00, 2.500000000E+00, 0.000000000E+00, 0.000000000E+00, 0.000000000E+00, 0.000000000E+00, -7.453750000E+02, 9.287239740E-01]), NASA9([6000.00, 20000.00], [ 3.396845420E+06, -2.194037652E+03, 3.080231878E+00, -8.068957550E-05, 6.252784910E-09, -2.574990067E-13, 4.429960218E-18, 1.650518960E+04, -4.048814390E+00])), transport=gas_transport(geom='atom', diam=2.576, well_depth=10.2), note='Ref-Elm. Moore NSRDS-NBS 35 1971; NSRDS-NBS 34 1970. [g 5/97]') #------------------------------------------------------------------------------- # Reaction data #------------------------------------------------------------------------------- # H2 REACTIONS # Reaction 1 three_body_reaction('H2 + M <=> H + H + M', [4.570000e+19, -1.4, 104380.0], efficiencies='AR:0.0 H2:2.5 H2O:12.0') # 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]) # 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='AR:0.0 H2:2.5 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='AR:0.0 H2:2.5 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='AR:0.75 H2:2.5 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='AR:0.0 H2:2.5 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='AR:0.0 H2:2.5 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