""" <><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><>! ----- 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. (2011). FUTURE REVISIONS/UPDATES MAY BE FOUND ON THE FUELS AND COMBUSTION RESEARCH LABORATORY WEBSITE: < http://www.princeton.edu/mae/people/faculty/dryer/homepage/combustion_lab/ > HOW TO CONTACT THE AUTHORS: Dr. Michael P. Burke R122 Building 200 Chemical Sciences and Engineering Division Argonne National Laboratory Argonne, IL 60439 Email: mpburke@anl.gov Prof. Frederick L. Dryer D-329D Engineering Quadrangle Mechanical and Aerospace Engineering Princeton University Princeton, NJ 08544 Phone: 609-258-5206 Lab: 609-258-0316 FAX: 609-258-1939 Email: fldryer@princeton.edu <><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><><>! Hong 2011 data except for CO and CO2 from NUIG 2013 """ units(length='cm', time='s', quantity='mol', act_energy='cal/mol') ideal_gas(name='gas', elements="H O N Ar He C", species="""H H2 O OH H2O O2 HO2 H2O2 N2 AR HE CO CO2""", 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, 7.05332819E-13, -1.99591964E-15, 2.30081632E-18, -9.27732332E-22, 2.54736599E+04, -4.46682853E-01]), NASA([1000.00, 3500.00], [ 2.50000001E+00, -2.30842973E-11, 1.61561948E-14, -4.73515235E-18, 4.98197357E-22, 2.54736599E+04, -4.46682914E-01])), transport=gas_transport(geom='atom', diam=2.05, well_depth=145.0), note='L7/88') species(name='H2', atoms='H:2', thermo=(NASA([200.00, 1000.00], [ 2.34433112E+00, 7.98052075E-03, -1.94781510E-05, 2.01572094E-08, -7.37611761E-12, -9.17935173E+02, 6.83010238E-01]), NASA([1000.00, 3500.00], [ 3.33727920E+00, -4.94024731E-05, 4.99456778E-07, -1.79566394E-10, 2.00255376E-14, -9.50158922E+02, -3.20502331E+00])), transport=gas_transport(geom='linear', diam=2.92, well_depth=38.0, polar=0.79, rot_relax=280.0), note='TPIS78') 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, 3500.00], [ 2.56942078E+00, -8.59741137E-05, 4.19484589E-08, -1.00177799E-11, 1.22833691E-15, 2.92175791E+04, 4.78433864E+00])), transport=gas_transport(geom='atom', diam=2.75, well_depth=80.0), note='L1/90') species(name='OH', atoms='O:1 H:1', thermo=(NASA([200.00, 1000.00], [ 3.99201543E+00, -2.40131752E-03, 4.61793841E-06, -3.88113333E-09, 1.36411470E-12, 3.37227356E+03, -1.03925458E-01]), NASA([1000.00, 3500.00], [ 3.09288767E+00, 5.48429716E-04, 1.26505228E-07, -8.79461556E-11, 1.17412376E-14, 3.61585000E+03, 4.47669610E+00])), transport=gas_transport(geom='linear', diam=2.75, well_depth=80.0), note='RUS78') species(name='H2O', atoms='O:1 H:2', thermo=(NASA([200.00, 1000.00], [ 4.19864056E+00, -2.03643410E-03, 6.52040211E-06, -5.48797062E-09, 1.77197817E-12, -3.02937267E+04, -8.49032208E-01]), NASA([1000.00, 3500.00], [ 3.03399249E+00, 2.17691804E-03, -1.64072518E-07, -9.70419870E-11, 1.68200992E-14, -3.00042971E+04, 4.96677010E+00])), transport=gas_transport(geom='nonlinear', diam=2.605, well_depth=572.4, dipole=1.844, rot_relax=4.0), note='L8/89') species(name='O2', atoms='O:2', thermo=(NASA([200.00, 1000.00], [ 3.78245636E+00, -2.99673416E-03, 9.84730201E-06, -9.68129509E-09, 3.24372837E-12, -1.06394356E+03, 3.65767573E+00]), NASA([1000.00, 3500.00], [ 3.28253784E+00, 1.48308754E-03, -7.57966669E-07, 2.09470555E-10, -2.16717794E-14, -1.08845772E+03, 5.45323129E+00])), transport=gas_transport(geom='linear', diam=3.458, well_depth=107.4, polar=1.6, rot_relax=3.8), note='TPIS89') 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], [ 4.27611269E+00, -5.42822417E-04, 1.67335701E-05, -2.15770813E-08, 8.62454363E-12, -1.77025821E+04, 3.43505074E+00]), NASA([1000.00, 3500.00], [ 4.16500285E+00, 4.90831694E-03, -1.90139225E-06, 3.71185986E-10, -2.87908305E-14, -1.78617877E+04, 2.91615662E+00])), transport=gas_transport(geom='nonlinear', diam=3.458, well_depth=107.4, rot_relax=3.8), note='L7/88') species(name='N2', atoms='N:2', thermo=(NASA([300.00, 1000.00], [ 3.29867700E+00, 1.40824040E-03, -3.96322200E-06, 5.64151500E-09, -2.44485400E-12, -1.02089990E+03, 3.95037200E+00]), NASA([1000.00, 5000.00], [ 2.92664000E+00, 1.48797680E-03, -5.68476000E-07, 1.00970380E-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='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, 4.36600000E+00]), NASA([1000.00, 5000.00], [ 2.50000000E+00, 0.00000000E+00, 0.00000000E+00, 0.00000000E+00, 0.00000000E+00, -7.45375000E+02, 4.36600000E+00])), transport=gas_transport(geom='atom', diam=3.33, well_depth=136.5), note='120186') 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') species(name='CO', atoms='C:1 O: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='C:1 O:2', 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') #------------------------------------------------------------------------------- # Reaction data #------------------------------------------------------------------------------- # ====================== # H2-O2 Chain Reactions # ====================== # Hong et al., Proc. Comb. Inst. 33:309-316 (2011) # Reaction 1 reaction('H + O2 <=> O + OH', [1.040000e+14, 0.0, 15286.0]) # Baulch et al., J. Phys. Chem. Ref. Data, 21:411 (1992) # Reaction 2 reaction('O + H2 <=> H + OH', [3.818000e+12, 0.0, 7948.0], options='duplicate') # Reaction 3 reaction('O + H2 <=> H + OH', [8.792000e+14, 0.0, 19170.0], options='duplicate') # Michael and Sutherland, J. Phys. Chem. 92:3853 (1988) # Reaction 4 reaction('H2 + OH <=> H2O + H', [2.160000e+08, 1.51, 3430.0]) # Baulch et al., J. Phys. Chem. Ref. Data, 21:411 (1992) # Reaction 5 reaction('OH + OH <=> O + H2O', [3.340000e+04, 2.42, -1930.0]) # ============================ # H2-O2 Dissociation Reactions # ============================ # Tsang and Hampson, J. Phys. Chem. Ref. Data, 15:1087 (1986) # Reaction 6 three_body_reaction('H2 + M <=> H + H + M', [4.577000e+19, -1.4, 104380.0], efficiencies='H2:2.5 H2O:12.0 AR:0.0 CO2:3.8 HE:0.0 CO:1.9') # Tsang and Hampson, J. Phys. Chem. Ref. Data, 15:1087 (1986) # Reaction 7 reaction('H2 + AR <=> H + H + AR', [5.840000e+18, -1.1, 104380.0]) # Reaction 8 reaction('H2 + HE <=> H + H + HE', [5.840000e+18, -1.1, 104380.0]) # Tsang and Hampson, J. Phys. Chem. Ref. Data, 15:1087 (1986) # Reaction 9 three_body_reaction('O + O + M <=> O2 + M', [6.165000e+15, -0.5, 0.0], efficiencies='H2:2.5 H2O:12.0 AR:0.0 CO2:3.8 HE:0.0 CO:1.9') # Tsang and Hampson, J. Phys. Chem. Ref. Data, 15:1087 (1986) # Reaction 10 reaction('O + O + AR <=> O2 + AR', [1.886000e+13, 0.0, -1788.0]) # Reaction 11 reaction('O + O + HE <=> O2 + HE', [1.886000e+13, 0.0, -1788.0]) # Tsang and Hampson, J. Phys. Chem. Ref. Data, 15:1087 (1986) # Reaction 12 three_body_reaction('O + H + M <=> OH + M', [4.714000e+18, -1.0, 0.0], efficiencies='H2:2.5 H2O:12.0 AR:0.75 CO2:3.8 HE:0.75 CO:1.9') # 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) # Reaction 13 three_body_reaction('H2O + M <=> H + OH + M', [6.064000e+27, -3.322, 120790.0], efficiencies='H2:3.0 N2:2.0 O2:1.5 H2O:0.0 CO2:3.8 HE:1.1 CO:1.9') # Efficiencies for CO and CO2 taken from Li et al., Int. J. Chem. Kinet. 36:566-575 (2004) # Srinivasan and Michael, Int. J. Chem. Kinetic. 38 (2006) # Reaction 14 reaction('H2O + H2O <=> H + OH + H2O', [1.006000e+26, -2.44, 120180.0]) # ================================= # 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) # Reaction 15 falloff_reaction('H + O2 (+ M) <=> HO2 (+ M)', kf=[4.650840e+12, 0.44, 0.0], kf0=[6.366000e+20, -1.72, 524.8], efficiencies='H2:2.0 O2:0.78 H2O:14.0 AR:0.67 CO2:3.8 HE:0.8 CO:1.9', falloff=Troe(A=0.5, T3=1e-30, T1=1e+30)) # ================================================================================= # 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 # Reaction 16 reaction('HO2 + H <=> H2 + O2', [2.750000e+06, 2.09, -1451.0]) # Mueller et al., Int. J. Chem. Kinetic. 31:113 (1999) # Reaction 17 reaction('HO2 + H <=> OH + OH', [7.079000e+13, 0.0, 295.0]) # 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 # Reaction 18 reaction('HO2 + O <=> O2 + OH', [2.850000e+10, 1.0, -723.93]) # Keyser, J. Phys. Chem. 92:1193 (1988) # Reaction 19 reaction('HO2 + OH <=> H2O + O2', [2.890000e+13, 0.0, -497.0]) # ===================================== # Formation and Consumption of H2O2 # ===================================== # Hippler et al., J. Chem. Phys. 93:1755 (1990) # Reaction 20 reaction('HO2 + HO2 <=> H2O2 + O2', [4.200000e+14, 0.0, 11982.0], options='duplicate') # Reaction 21 reaction('HO2 + HO2 <=> H2O2 + O2', [1.300000e+11, 0.0, -1629.3], options='duplicate') # Troe, Combust. Flame, 158:594-601 (2011) # Rate constant is for Ar # Reaction 22 falloff_reaction('H2O2 (+ M) <=> OH + OH (+ M)', kf=[2.000000e+12, 0.9, 48749.0], kf0=[2.490000e+24, -2.3, 48749.0], efficiencies='N2:1.5 H2:3.7 O2:1.2 H2O:7.5 H2O2:7.7 CO2:1.6 HE:0.65 CO:2.8', falloff=Troe(A=0.43, T3=1e-30, T1=1e+30)) # Efficiencies for H2 and CO taken from Li et al., Int. J. Chem. Kinet. 36:566-575 (2004) # Tsang and Hampson, J. Phys. Chem. Ref. Data, 15:1087 (1986) # Reaction 23 reaction('H2O2 + H <=> H2O + OH', [2.410000e+13, 0.0, 3970.0]) # Reaction 24 reaction('H2O2 + H <=> HO2 + H2', [4.820000e+13, 0.0, 7950.0]) # Reaction 25 reaction('H2O2 + O <=> OH + HO2', [9.550000e+06, 2.0, 3970.0]) # Hong et al., J. Phys. Chem. A 114 (2010) 57185727 # Reaction 26 reaction('H2O2 + OH <=> HO2 + H2O', [1.740000e+12, 0.0, 318.0], options='duplicate') # Reaction 27 reaction('H2O2 + OH <=> HO2 + H2O', [7.590000e+13, 0.0, 7270.0], options='duplicate')