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reactions.py
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reactions.py
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#!/usr/bin/env python
# encoding: utf-8
name = "Deutschmann2006_adjusted"
shortDesc = u""
longDesc = u"""
test surface mechanism: based upon Olaf Deutschmann's work:
"Modeling the high-temperature catalytic partial oxidation of methane over platinum gauze: Detailed gas-phase and surface chemistries coupled with 3D flow field simulations"
Quiceno et al
Applied Catalysis, 2006, 303, 166-176
In this "adjusted" library, eight of the reactions have had their barriers
raised to match the endothermicity of the reaction, using our RMG-estimated thermochemistry.
These are noted in the longDesc fields of the reactions.
"""
# Reverse of R9
entry(
index = 1,
label = "H2 + Pt + Pt <=> HX + HX",
kinetics = StickingCoefficient(
A = 4.6E-2,
n = 0,
Ea=(0, 'J/mol'),
Tmin = (200, 'K'),
Tmax = (3000, 'K'),
coverage_dependence = {'Pt': {'a': 0.0, 'm': -1.0, 'E': (0.0, 'J/mol')}},
),
shortDesc = u"""Default""",
longDesc = u"""R1""",
metal = "Pt",
)
#CFG: O2 is a special case: we need to treat it separately
# reverse of R10
# entry(
# index = 2,
# label = "O2 + Pt + Pt <=> OX + OX",
# kinetics = SurfaceArrhenius(
# A=(1.89E21, 'cm^5/(mol^2*s)'),
# n = -0.5,
# Ea=(0.0, 'J/mol'),
# Tmin = (200, 'K'),
# Tmax = (3000, 'K'),
# ),
# shortDesc = u"""Default""",
# longDesc = u"""R2""",
# metal = "Pt",
# )
# reverse of R34
# entry(
# index = 3,
# label = "CH4 + Pt + Pt <=> CH3X + HX",
# kinetics = StickingCoefficient(
# A = 9.0E-4,
# n = 0,
# Ea=(72000, 'J/mol'),
# Tmin = (200, 'K'),
# Tmax = (3000, 'K'),
# ),
# shortDesc = u"""Default""",
# longDesc = u"""R3""",
# metal = "Pt",
# )
# reverse of R36
entry(
index = 4,
label = "CH4 + OX + Pt <=> CH3X + HOX",
kinetics = SurfaceArrhenius(
A=(5.0E18, 'cm^5/(mol^2*s)'),
n = 0.7,
Ea=(42000.0, 'J/mol'),
Tmin = (200, 'K'),
Tmax = (3000, 'K'),
coverage_dependence = {'OX': {'a': 0.0, 'm': 0.0, 'E': (8000, 'J/mol')}},
),
shortDesc = u"""Default""",
longDesc = u"""R4. Epsilon written as -8 kJ/mol in paper, but +8 kJ/mol in
published chemkin file""",
metal = "Pt",
)
# reverse of R35
entry(
index = 5,
label = "CH4 + HOX + Pt <=> CH3X + H2OX",
kinetics = StickingCoefficient(
A = 1.0,
n = 0,
Ea=(10000, 'J/mol'),
Tmin = (200, 'K'),
Tmax = (3000, 'K'),
),
shortDesc = u"""Default""",
longDesc = u"""R5""",
metal = "Pt",
)
entry(
index = 6,
label = "H2O + Pt <=> H2OX",
kinetics = StickingCoefficient(
A = 7.5E-1,
n = 0,
Ea=(0, 'J/mol'),
Tmin = (200, 'K'),
Tmax = (3000, 'K'),
),
shortDesc = u"""Default""",
longDesc = u"""R6. H2OX is vdW H2O.""",
metal = "Pt",
)
entry(
index = 7,
label = "CO2 + Pt <=> CO2X",
kinetics = StickingCoefficient(
A = 5.0E-3,
n = 0,
Ea=(0, 'J/mol'),
Tmin = (200, 'K'),
Tmax = (3000, 'K'),
),
shortDesc = u"""Default""",
longDesc = u"""R7. H2OX is vdW CO2.""",
metal = "Pt",
)
#CFG: CO is a special case: we need to treat it separately
# entry(
# index = 8,
# label = "CO + Pt <=> OCX",
# kinetics = StickingCoefficient(
# A = 8.4E-1,
# n = 0,
# Ea=(0, 'J/mol'),
# Tmin = (200, 'K'),
# Tmax = (3000, 'K'),
# ),
# shortDesc = u"""Default""",
# longDesc = u"""R8""",
# metal = "Pt",
# )
#endothermic - reverse of R1
# entry(
# index = 9,
# label = "HX + HX <=> Pt + Pt + H2",
# kinetics = SurfaceArrhenius(
# A=(3.7E17, 'm^2/(mol*s)'),
# n = 0,
# Ea=(67400.0, 'J/mol'),
# Tmin = (200, 'K'),
# Tmax = (3000, 'K'),
# coverage_dependence = {'HX': {'a': 0.0, 'm': 0.0, 'E': (-10000.0, 'J/mol')}},
# ),
# shortDesc = u"""Default""",
# longDesc = u"""R9""",
# metal = "Pt",
# )
#endothermic - reverse of R2
entry(
index = 10,
label = "OX + OX <=> Pt + Pt + O2",
kinetics = SurfaceArrhenius(
A=(3.7E17, 'm^2/(mol*s)'),
n = 0,
Ea=(278700.0, 'J/mol'),
Tmin = (200, 'K'),
Tmax = (3000, 'K'),
coverage_dependence = {'OX': {'a': 0.0, 'm': 0.0, 'E': (-188280, 'J/mol')}},
),
shortDesc = u"""Default""",
longDesc = u"""R10. Ea raised from 235.5 to 278.7 kJ/mol to match
endothermicity of reaction.""",
metal = "Pt",
)
#endothermic - reverse of R6
#entry(
# index = 11,
# label = "H2OX <=> H2O + Pt",
# kinetics = SurfaceArrhenius(
# A=(4.5E8, 'm^2/(mol*s)'),
# n = 0,
# Ea=(41800.0, 'J/mol'),
# Tmin = (200, 'K'),
# Tmax = (3000, 'K'),
# ),
# shortDesc = u"""Default""",
# longDesc = u"""R11. H2OX is vdW H2O.""",
# metal = "Pt",
#)
#endothermic - reverse of R8
entry(
index = 12,
label = "OCX <=> CO + Pt",
kinetics = SurfaceArrhenius(
A=(1.0E11, '1/s'),
n = 0,
Ea=(169500.0, 'J/mol'),
Tmin = (200, 'K'),
Tmax = (3000, 'K'),
coverage_dependence = {'OCX': {'a': 0.0, 'm': 0.0, 'E': (-33000, 'J/mol')}},
),
shortDesc = u"""Default""",
longDesc = u"""R12. Ea raised from 146.0 to 169.5 kJ/mol to match
endothermicity of reaction.""",
metal = "Pt",
)
#endothermic - reverse of R7
# entry(
# index = 13,
# label = "CO2X <=> CO2 + Pt",
# kinetics = SurfaceArrhenius(
# A=(1.0E9, 'm^2/(mol*s)'),
# n = 0,
# Ea=(33800.0, 'J/mol'),
# Tmin = (200, 'K'),
# Tmax = (3000, 'K'),
# ),
# shortDesc = u"""Default""",
# longDesc = u"""R13. CO2X is vdW CO2. Ea raised from 27.1 to 33.8 kJ/mol to
# match endothermicity of reaction.""",
# metal = "Pt",
# )
# reverse of R15
# entry(
# index = 14,
# label = "CX + OX <=> OCX + Pt",
# kinetics = SurfaceArrhenius(
# A=(3.7E19, 'cm^2/(mol*s)'),
# n = 0,
# Ea=(0, 'J/mol'),
# Tmin = (200, 'K'),
# Tmax = (3000, 'K'),
# ),
# shortDesc = u"""Default""",
# longDesc = u"""R14""",
# metal = "Pt",
# )
#endothermic - reverse of R14
entry(
index = 15,
label = "OCX + Pt <=> CX + OX",
kinetics = SurfaceArrhenius(
A=(3.7E15, 'm^2/(mol*s)'),
n = 0,
Ea=(236500, 'J/mol'),
Tmin = (200, 'K'),
Tmax = (3000, 'K'),
coverage_dependence = {'OCX': {'a': 0.0, 'm': 0.0, 'E': (-33000, 'J/mol')}},
),
shortDesc = u"""Default""",
longDesc = u"""R15""",
metal = "Pt",
)
#There is an error in the paper. This value is consistent with the file on the DETCHEM mechanisms website.
entry(
index = 16,
label = "OCX + OX <=> CO2X + Pt",
kinetics = SurfaceArrhenius(
A=(3.7E21, 'cm^2/(mol*s)'),
n = 0,
Ea=(117600, 'J/mol'),
Tmin = (200, 'K'),
Tmax = (3000, 'K'),
coverage_dependence = {'OCX': {'a': 0.0, 'm': 0.0, 'E': (-33000, 'J/mol')}},
),
shortDesc = u"""Default""",
longDesc = u"""R16. CO2X is vdW CO2.
The table in the paper pdf says 3.7e19, but the supplementary material has 3.7e21,
which is apparently correct and the paper is wrong.
""",
metal = "Pt",
)
#endothermic - reverse of R16
# entry(
# index = 17,
# label = "CO2X + Pt <=> OCX + OX",
# kinetics = SurfaceArrhenius(
# A=(3.7E15, 'm^2/(mol*s)'),
# n = 0,
# Ea=(173300, 'J/mol'),
# Tmin = (200, 'K'),
# Tmax = (3000, 'K'),
# coverage_dependence = {'OX': {'a': 0.0, 'm': 0.0, 'E': (94140, 'J/mol')}},
# ),
# shortDesc = u"""Default""",
# longDesc = u"""R17. CO2X is vdW CO2.""",
# metal = "Pt",
# )
#endothermic - reverse of R19
entry(
index = 18,
label = "OCX + HOX <=> CO2X + HX",
kinetics = SurfaceArrhenius(
A=(1.0E15, 'm^2/(mol*s)'),
n = 0,
Ea=(38700, 'J/mol'),
Tmin = (200, 'K'),
Tmax = (3000, 'K'),
coverage_dependence = {'OCX': {'a': 0.0, 'm': 0.0, 'E': (-30000, 'J/mol')}},
),
shortDesc = u"""Default""",
longDesc = u"""R18. CO2X is vdW CO2.""",
metal = "Pt",
)
# reverse of R18
# entry(
# index = 19,
# label = "CO2X + HX <=> OCX + HOX",
# kinetics = SurfaceArrhenius(
# A=(1.0E19, 'cm^2/(mol*s)'),
# n = 0,
# Ea=(14900, 'J/mol'),
# Tmin = (200, 'K'),
# Tmax = (3000, 'K'),
# ),
# shortDesc = u"""Default""",
# longDesc = u"""R19. CO2X is vdW CO2. Ea raised from 27.1 to 33.8 kJ/mol to
# match endothermicity of reaction.""",
# metal = "Pt",
# )
#endothermic - reverse of R21
#entry(
# index = 20,
# label = "CH3X + Pt <=> CH2X + HX",
# kinetics = SurfaceArrhenius(
# A=(1.26E18, 'm^2/(mol*s)'),
# n = 0,
# Ea=(70300, 'J/mol'),
# Tmin = (200, 'K'),
# Tmax = (3000, 'K'),
# ),
# shortDesc = u"""Default""",
# longDesc = u"""R20""",
# metal = "Pt",
#)
entry(
index = 21,
label = "CH2X + HX <=> CH3X + Pt",
kinetics = SurfaceArrhenius(
A=(3.09E22, 'cm^2/(mol*s)'),
n = 0,
Ea=(0, 'J/mol'),
Tmin = (200, 'K'),
Tmax = (3000, 'K'),
coverage_dependence = {'HX': {'a': 0.0, 'm': 0.0, 'E': (-2800, 'J/mol')}},
),
shortDesc = u"""Default""",
longDesc = u"""R21""",
metal = "Pt",
)
#endothermic - reverse of R23
entry(
index = 22,
label = "CH2X + Pt <=> CHX + HX",
kinetics = SurfaceArrhenius(
A=(7.31E18, 'm^2/(mol*s)'),
n = 0,
Ea=(58900, 'J/mol'),
Tmin = (200, 'K'),
Tmax = (3000, 'K'),
coverage_dependence = {'CX': {'a': 0.0, 'm': 0.0, 'E': (50000, 'J/mol')}},
),
shortDesc = u"""Default""",
longDesc = u"""R22""",
metal = "Pt",
)
# entry(
# index = 23,
# label = "CHX + HX <=> CH2X + Pt",
# kinetics = SurfaceArrhenius(
# A=(3.09E22, 'cm^2/(mol*s)'),
# n = 0,
# Ea=(53400, 'J/mol'),
# Tmin = (200, 'K'),
# Tmax = (3000, 'K'),
# coverage_dependence = {'HX': {'a': 0.0, 'm': 0.0, 'E': (-2800, 'J/mol')}},
# ),
# shortDesc = u"""Default""",
# longDesc = u"""R23. Ea raised from 0.0 to 53.4 kJ/mol to match
# endothermicity of reaction.""",
# metal = "Pt",
# )
entry(
index = 24,
label = "CHX + Pt <=> CX + HX",
kinetics = SurfaceArrhenius(
A=(3.09E22, 'cm^2/(mol*s)'),
n = 0,
Ea=(51700, 'J/mol'),
Tmin = (200, 'K'),
Tmax = (3000, 'K'),
coverage_dependence = {'HX': {'a': 0.0, 'm': 0.0, 'E': (-2800, 'J/mol')}},
),
shortDesc = u"""Default""",
longDesc = u"""R24. Ea raised from 0.0 to 51.7 kJ/mol to match
endothermicity of reaction.""",
metal = "Pt",
)
#endothermic - reverse of R24
#entry(
# index = 25,
# label = "CX + HX <=> CHX + Pt",
# kinetics = SurfaceArrhenius(
# A=(1.25E18, 'm^2/(mol*s)'),
# n = 0,
# Ea=(138000, 'J/mol'),
# Tmin = (200, 'K'),
# Tmax = (3000, 'K'),
# ),
# shortDesc = u"""Default""",
# longDesc = u"""R25""",
# metal = "Pt",
#)
# reverse of R27
# entry(
# index = 26,
# label = "HX + OX <=> HOX + Pt",
# kinetics = SurfaceArrhenius(
# A=(1.28E21, 'cm^2/(mol*s)'),
# n = 0,
# Ea=(11200, 'J/mol'),
# Tmin = (200, 'K'),
# Tmax = (3000, 'K'),
# ),
# shortDesc = u"""Default""",
# longDesc = u"""R26""",
# metal = "Pt",
# )
#endothermic - reverse of R26
entry(
index = 27,
label = "HOX + Pt <=> HX + OX",
kinetics = SurfaceArrhenius(
A=(7.39E15, 'm^2/(mol*s)'),
n = 0,
Ea=(77300, 'J/mol'),
Tmin = (200, 'K'),
Tmax = (3000, 'K'),
coverage_dependence = {'OX': {'a': 0.0, 'm': 0.0, 'E': (-73220, 'J/mol')}},
),
shortDesc = u"""Default""",
longDesc = u"""R27""",
metal = "Pt",
)
#endothermic - reverse of R33
entry(
index = 28,
label = "H2OX + Pt <=> HX + HOX",
kinetics = SurfaceArrhenius(
A=(1.15E15, 'm^2/(mol*s)'),
n = 0,
Ea=(101400, 'J/mol'),
Tmin = (200, 'K'),
Tmax = (3000, 'K'),
coverage_dependence = {'OX': {'a': 0.0, 'm': 0.0, 'E': (167360, 'J/mol')}},
),
shortDesc = u"""Default""",
longDesc = u"""R28. H2OX is vdW H2O.""",
metal = "Pt",
)
#endothermic - reverse of R30
#entry(
# index = 29,
# label = "HOX + HOX <=> H2OX + OX",
# kinetics = SurfaceArrhenius(
# A=(7.4E16, 'm^2/(mol*s)'),
# n = 0,
# Ea=(74000, 'J/mol'),
# Tmin = (200, 'K'),
# Tmax = (3000, 'K'),
# ),
# shortDesc = u"""Default""",
# longDesc = u"""R29. H2OX is vdW H2O.""",
# metal = "Pt",
#)
entry(
index = 30,
label = "H2OX + OX <=> HOX + HOX",
kinetics = SurfaceArrhenius(
A=(1.0E20, 'cm^2/(mol*s)'),
n = 0,
Ea=(90500, 'J/mol'),
Tmin = (200, 'K'),
Tmax = (3000, 'K'),
coverage_dependence = {'OX': {'a': 0.0, 'm': 0.0, 'E': (-240580, 'J/mol')}},
),
shortDesc = u"""Default""",
longDesc = u"""R30. H2OX is vdW H2O. Ea raised from 43.1 to 90.5 kJ/mol to
match endothermicity of reaction.""",
metal = "Pt",
)
entry(
index = 31,
label = "H2 + CX <=> CH2X",
kinetics = StickingCoefficient(
A = 4.0E-2,
n = 0,
Ea=(29700, 'J/mol'),
Tmin = (200, 'K'),
Tmax = (3000, 'K'),
coverage_dependence = {'CX': {'a': 0.0, 'm': 0.0, 'E': (4600, 'J/mol')}},
),
shortDesc = u"""Default""",
longDesc = u"""R31""",
metal = "Pt",
)
# - reverse of R31
# entry(
# index = 32,
# label = "CH2X <=> H2 + CX",
# kinetics = SurfaceArrhenius(
# A=(7.69E13, '1/s'),
# n = 0,
# Ea=(46300, 'J/mol'),
# Tmin = (200, 'K'),
# Tmax = (3000, 'K'),
# coverage_dependence = {'CX': {'a': 0.0, 'm': 0.0, 'E': (50000, 'J/mol')}},
# ),
# shortDesc = u"""Default""",
# longDesc = u"""R32. Ea raised from 25.1 to 46.3 kJ/mol to match
# endothermicity of reaction.""",
# metal = "Pt",
# )
# reverse of R28
# entry(
# index = 33,
# label = "HX + HOX <=> H2OX + Pt",
# kinetics = SurfaceArrhenius(
# A=(2.04E21, 'cm^2/(mol*s)'),
# n = 0,
# Ea=(66220, 'J/mol'),
# Tmin = (200, 'K'),
# Tmax = (3000, 'K'),
# ),
# shortDesc = u"""Default""",
# longDesc = u"""R33. H2OX is vdW H2O.""",
# metal = "Pt",
# )
# reverse of R3
entry(
index = 34,
label = "CH3X + HX <=> CH4 + Pt + Pt",
kinetics = SurfaceArrhenius(
A=(3.3E21, 'cm^2/(mol*s)'),
n = 0,
Ea=(50000, 'J/mol'),
Tmin = (200, 'K'),
Tmax = (3000, 'K'),
coverage_dependence = {'HX': {'a': 0.0, 'm': 0.0, 'E': (-28000, 'J/mol')}},
),
shortDesc = u"""Default""",
longDesc = u"""R34""",
metal = "Pt",
)
#endothermic - reverse of R5
#entry(
# index = 35,
# label = "CH3X + H2OX <=> CH4 + HOX + Pt",
# kinetics = SurfaceArrhenius(
# A=(3.7E17, 'm^2/(mol*s)'),
# n = 0,
# Ea=(110600, 'J/mol'),
# Tmin = (200, 'K'),
# Tmax = (3000, 'K'),
# ),
# shortDesc = u"""Default""",
# longDesc = u"""R35. H2OX is vdW H2O.""",
# metal = "Pt",
#)
#endothermic - reverse of R4
#entry(
# index = 36,
# label = "CH3X + HOX <=> CH4 + OX + Pt",
# kinetics = SurfaceArrhenius(
# A=(3.7E17, 'm^2/(mol*s)'),
# n = 0,
# Ea=(87900, 'J/mol'),
# Tmin = (200, 'K'),
# Tmax = (3000, 'K'),
# ),
# shortDesc = u"""Default""",
# longDesc = u"""R36""",
# metal = "Pt",
#)