############################################################
#
# Z46, methane mechanism
#
# Developed by N. Zettervall
# 2022-05-02, FOI, Sweden
#
# Report number: FOI-D–1152–SE
#
############################################################
#
# Thermo data from GOOS BURCAT
# Transport data from USCII C2H4
#

units(length = “cm”, time = “s”, quantity = “mol”, act_energy = “cal/mol”)

ideal_gas(name = “gas”,
elements = ” H O C N “,
species = “”” CH4 O2 N2 H2O CO2 H O OH HO2 H2
CO H2O2 HCO CH2O CH3 CH3O CH2 CH “””,
reactions = “all”,
transport = “Mix”,
initial_state = state(temperature = 300.0,
pressure = OneAtm) )

####################################################################################

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=’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=’OH’,
atoms=’H:1 O: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=’HYDROXYLRADIIU3/03′)

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, 6000.00],
[ 2.93286575E+00, 8.26608026E-04, -1.46402364E-07,
1.54100414E-11, -6.88804800E-16, -8.13065581E+02,
-1.02432865E+00])),
transport=gas_transport(geom=’linear’,
diam=2.92,
well_depth=38.0,
polar=0.79,
rot_relax=280.0),
note=’REFELEMENTtpis78′)

species(name=’H2O’,
atoms=’H:2 O:1′,
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=’HO2′,
atoms=’H:1 O:2′,
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=’H:2 O: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=’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=’REFELEMENTG8/02′)

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, 6000.00],
[ 3.66096065E+00, 6.56365811E-04, -1.41149627E-07,
2.05797935E-11, -1.29913436E-15, -1.21597718E+03,
3.41536279E+00])),
transport=gas_transport(geom=’linear’,
diam=3.458,
well_depth=107.4,
polar=1.6,
rot_relax=3.8),
note=’REFELEMENTRUS89′)

species(name=’CH4′,
atoms=’H:4 C:1′,
thermo=(NASA([200.00, 1000.00],
[ 5.14825732E+00, -1.37002410E-02, 4.93749414E-05,
-4.91952339E-08, 1.70097299E-11, -1.02453222E+04,
-4.63322726E+00]),
NASA([1000.00, 6000.00],
[ 1.91178600E+00, 9.60267960E-03, -3.38387841E-06,
5.38797240E-10, -3.19306807E-14, -1.00992136E+04,
8.48241861E+00])),
transport=gas_transport(geom=’nonlinear’,
diam=3.746,
well_depth=141.4,
polar=2.6,
rot_relax=13.0),
note=’RRHOg8/99′)

species(name=’CH3′,
atoms=’H:3 C:1′,
thermo=(NASA([200.00, 1000.00],
[ 3.65717970E+00, 2.12659790E-03, 5.45838830E-06,
-6.61810030E-09, 2.46570740E-12, 1.64227160E+04,
1.67353540E+00]),
NASA([1000.00, 6000.00],
[ 2.97812060E+00, 5.79785200E-03, -1.97558000E-06,
3.07297900E-10, -1.79174160E-14, 1.65095130E+04,
4.72247990E+00])),
transport=gas_transport(geom=’linear’,
diam=3.8,
well_depth=144.0),
note=’IU0702′)

species(name=’CH2′,
atoms=’H:2 C:1′,
thermo=(NASA([200.00, 1000.00],
[ 4.19331325E+00, -2.33105184E-03, 8.15676451E-06,
-6.62985981E-09, 1.93233199E-12, 5.03662246E+04,
-7.46734310E-01]),
NASA([1000.00, 6000.00],
[ 3.13501686E+00, 2.89593926E-03, -8.16668090E-07,
1.13572697E-10, -6.36262835E-15, 5.05040504E+04,
4.06030621E+00])),
transport=gas_transport(geom=’linear’,
diam=3.8,
well_depth=144.0),
note=’SINGLETIU3/03′)

species(name=’CH’,
atoms=’H:1 C:1′,
thermo=(NASA([200.00, 1000.00],
[ 3.48975830E+00, 3.24321600E-04, -1.68997510E-06,
3.16284200E-09, -1.40618030E-12, 7.06607550E+04,
2.08428410E+00]),
NASA([1000.00, 6000.00],
[ 2.52093690E+00, 1.76536390E-03, -4.61476600E-07,
5.92896750E-11, -3.34745010E-15, 7.09948780E+04,
7.40518290E+00])),
transport=gas_transport(geom=’linear’,
diam=2.75,
well_depth=80.0),
note=’IU3/03′)

species(name=’CH3O’,
atoms=’H:3 C:1 O:1′,
thermo=(NASA([200.00, 1000.00],
[ 3.71180502E+00, -2.80463306E-03, 3.76550971E-05,
-4.73072089E-08, 1.86588420E-11, 1.30772484E+03,
6.57240864E+00]),
NASA([1000.00, 6000.00],
[ 4.75779238E+00, 7.44142474E-03, -2.69705176E-06,
4.38090504E-10, -2.63537098E-14, 3.90139164E+02,
-1.96680028E+00])),
transport=gas_transport(geom=’nonlinear’,
diam=3.69,
well_depth=417.0,
dipole=1.7,
rot_relax=2.0),
note=’METHOXYRADIU1/03′)

species(name=’CH2O’,
atoms=’H:2 C:1 O:1′,
thermo=(NASA([200.00, 1000.00],
[ 4.79372312E+00, -9.90833322E-03, 3.73219990E-05,
-3.79285237E-08, 1.31772641E-11, -1.43227879E+04,
6.02798058E-01]),
NASA([1000.00, 6000.00],
[ 3.16952665E+00, 6.19320560E-03, -2.25056366E-06,
3.65975660E-10, -2.20149458E-14, -1.44922756E+04,
6.04207898E+00])),
transport=gas_transport(geom=’nonlinear’,
diam=3.59,
well_depth=498.0,
rot_relax=2.0),
note=’Formaldehydeg8/88′)

species(name=’HCO’,
atoms=’H:1 C:1 O:1′,
thermo=(NASA([200.00, 1000.00],
[ 4.23754610E+00, -3.32075257E-03, 1.40030264E-05,
-1.34239995E-08, 4.37416208E-12, 3.87241185E+03,
3.30834869E+00]),
NASA([1000.00, 6000.00],
[ 3.92001542E+00, 2.52279324E-03, -6.71004164E-07,
1.05615948E-10, -7.43798261E-15, 3.65342928E+03,
3.58077056E+00])),
transport=gas_transport(geom=’nonlinear’,
diam=3.59,
well_depth=498.0),
note=’T5/03′)

species(name=’CO’,
atoms=’C:1 O:1′,
thermo=(NASA([200.00, 1000.00],
[ 3.57953350E+00, -6.10353690E-04, 1.01681430E-06,
9.07005860E-10, -9.04424490E-13, -1.43440860E+04,
3.50840930E+00]),
NASA([1000.00, 6000.00],
[ 3.04848590E+00, 1.35172810E-03, -4.85794050E-07,
7.88536440E-11, -4.69807460E-15, -1.42661170E+04,
6.01709770E+00])),
transport=gas_transport(geom=’linear’,
diam=3.65,
well_depth=98.1,
polar=1.95,
rot_relax=1.8),
note=’RUS79′)

species(name=’CO2′,
atoms=’C:1 O:2′,
thermo=(NASA([200.00, 1000.00],
[ 2.35681300E+00, 8.98412990E-03, -7.12206320E-06,
2.45730080E-09, -1.42885480E-13, -4.83719710E+04,
9.90090350E+00]),
NASA([1000.00, 6000.00],
[ 4.63651110E+00, 2.74145690E-03, -9.95897590E-07,
1.60386660E-10, -9.16198570E-15, -4.90249040E+04,
-1.93489550E+00])),
transport=gas_transport(geom=’linear’,
diam=3.763,
well_depth=244.0,
polar=2.65,
rot_relax=2.1),
note=’L7/88′)

########################## Z46 ##############################

reaction( “H + O2 => OH + O”, [1.55E+14, 0, 16800])
reaction( “OH + O => H + O2”, [1.2E+13, 0, 690])
reaction( “O + H2 => OH + H”, [1.80000E+10, 1, 8826])
reaction( “OH + H => O + H2”, [8.00000E+09, 1, 6760])
reaction( “H2 + OH => H2O + H”, [1.17000E+09, 1.3, 3626])
reaction( “H2O + H => H2 + OH”, [5.09000E+09, 1.3, 18588])
reaction( “OH + OH => O + H2O”, [6.00000E+08, 1.3, 0])
reaction( “O + H2O => OH + OH”, [5.90000E+09, 1.3, 17029])
three_body_reaction( “H + O2 + M => HO2 + M”, [1.6E+18, -0.8, 0],
efficiencies = ” CH4:6.5 CO:0.75 CO2:1.5 H2:1 H2O:6.5 N2:0.4 O2:0.4 “)
reaction( “H + HO2 => OH + OH”, [1.50000E+14, 0, 1004])
reaction( “H + HO2 => H2 + O2”, [2.50000E+13, 0, 700])
reaction( “OH + HO2 => H2O + O2”, [2.00000E+13, 0, 1000])
reaction( “CO + OH => CO2 + H”, [1.51000E+07, 1.3, -758])
reaction( “CO2 + H => CO + OH”, [1.57E+09, 1.3, 21000])
falloff_reaction( “CH4 (+ M) => CH3 + H (+ M)”,
kf = [6.30000E+14, 0, 104000],
kf0 = [1.00000E+17, 0, 86000],
efficiencies = ” CH4:6.5 CO:0.75 CO2:1.5 H2:1 H2O:6.5 N2:0.4 O2:0.4 “)
falloff_reaction( “CH3 + H (+ M) => CH4 (+ M)”,
kf = [5.20000E+12, 0, -1310],
kf0 = [8.25000E+14, 0, -19310],
efficiencies = ” CH4:6.5 CO:0.75 CO2:1.5 H2:1 H2O:6.5 N2:0.4 O2:0.4 “)
reaction( “CH4 + H => CH3 + H2”, [2.20000E+04, 3, 8750])
reaction( “CH3 + H2 => CH4 + H”, [9.57000E+02, 3, 8750])
reaction( “CH4 + OH => CH3 + H2O”, [1.60000E+06, 2.1, 2460])
reaction( “CH3 + H2O => CH4 + OH”, [3.02000E+05, 2.1, 17422])
reaction( “CH3 + O => CH2O + H”, [6.80000E+13, 0, 0])
reaction( “CH2O + H => HCO + H2”, [9.0E+13, 0, 3991])
reaction( “CH2O + OH => HCO + H2O”, [3.00000E+13, 0, 1195])
reaction( “HCO + H => CO + H2”, [4.00000E+13, 0, 0])
three_body_reaction( “HCO + M => CO + H + M”, [1.60000E+14, 0, 14700])
reaction( “CH3 + O2 => CH3O + O”, [4.0E+13, 0, 25652])
reaction( “CH3O + H => CH2O + H2”, [2.00000E+13, 0, 0])
three_body_reaction( “CH3O + M => CH2O + H + M”, [2.40000E+13, 0, 28812])
reaction( “HO2 + HO2 => H2O2 + O2”, [8.0E+13, 0, 0])
three_body_reaction( “H2O2 + M => OH + OH + M”, [1.30000E+17, 0, 45500])
three_body_reaction( “OH + OH + M => H2O2 + M”, [9.86000E+14, 0, -5070])
reaction( “H2O2 + OH => H2O + HO2”, [1.00000E+13, 0, 1800])
reaction( “H2O + HO2 => H2O2 + OH”, [2.86000E+13, 0, 32790])
three_body_reaction( “OH + H + M => H2O + M”, [2.20000E+22, -2, 0])
three_body_reaction( “H + H + M => H2 + M”, [1.80000E+18, -1, 0])
reaction( ” CH3 + OH => CH2 + H2O “, [7.6E+06, 2.0, 5000])
reaction( ” CH2 + O => CO + H2 “, [3.0E+13, 0, 0])
reaction( ” CH2 + OH => CH + H2O “, [1.13E+07, 2.0, 3000])
reaction( ” CH + O => CO + H “, [5.7E+13, 0, 0])
reaction( ” CH + OH => HCO + H “, [3.0E+13, 0, 0])
reaction( ” CH + O2 => HCO + O “, [3.3E+13, 0, 0])
reaction( ” CH + CO2 => HCO + CO “, [8.4E+13, 0, 200])
reaction(‘CH4 + HO2 => CH3 + H2O2’, [1.130000e+01, 3.74, 14010.0])
reaction(‘CH3 + HO2 => CH4 + O2’, [1.160000e+05, 2.23, -3022.0])
three_body_reaction( “CO2 + M => CO + O + M”, [0.1E+11, 0, 45500])
reaction(‘CH4 + O2 => CH3 + HO2’, [1.0e+05, 2.23, 58000.0])