
#
#    HACA Mechanism - very rough prototype
#              Reference:
#     (1)  M. Frenklach, H. Wang,
#          "Detailed Mechanism and Modeling of Soot Particle Formation"
#          in Soot Formation in Combustion: Mechanisms and Models"
#          J. Bockhorn Ed., Springer Verlag, Heidelberg (1994).
#
#
# HKM Notes -> The elements in the element arrays all have to be equal and
#              in the same order. This is a limitation of cads.

units(length = 'cm', quantity = 'mol', act_energy = 'kcal/mol')

#------------- the gas -------------------------------------

ideal_gas(name = 'gas',
          elements = 'O H C N Ar',
          species = 'gri30: H N2 CH3 CH4 C2H2 H2 OH H2O CO O2',
          initial_state = state(temperature = 1400.0,
                                pressure = OneAtm,
                    mole_fractions = 'H:0.01, N2:0.8899, H2:0.04, CH4:0.01 C2H2:0.01 \
                                      OH:0.0001 H2O:0.04 O2:0.001'))


#------------- bulk soot -------------------------------------
# Taken from Bensen's book. 
# However, entropy is negative; this is not correct.
# Group contribution approach needs to be modified. Bensen has a
# negative value for S here, because the group contribution is usually
# lumped in with other groups which have positive S contributions.
# However, for the current mechanism, bulk thermodynamics doesn't
# matter since all reactions involving bulk growth or etching
# are irreversible.
#
stoichiometric_solid(name = 'soot',
                     elements = 'O H C N Ar',
                     density = (3.52, 'g/cm3'),
                     species = 'CB-CB3')

species(name = 'CB-CB3',
        atoms = 'C:1',
        thermo = const_cp(t0  = (1000., 'K'),
                          h0  = (9.22, 'kcal/mol')  ,
                          s0  = (-3.02, 'cal/mol/K'),
                          cp0 = (5.95, 'cal/mol/K') ))

#------------- the diamond surface -------------------------------------
#
# Site density taken from Frenklach/Wang p. 179.
#
ideal_interface(name = 'soot_interface',
	        elements = 'O H C N Ar ',
	        species = 'Csoot-* Csoot-H',
                reactions = 'all',
                phases = 'gas soot',
                site_density = (3.8E-9, 'mol/cm2'),
                initial_state = state(temperature= 1000.0,
                                      coverages = 'Csoot-*:0.1, Csoot-H:0.9'))

# HKM -> Note, thermo from the following source:
# 'S. J. Harris and D. G. Goodwin, 'Growth on
# the reconstructed diamond (100) surface, 'J. Phys. Chem. vo. 97,
# 23-28 (1993). reactions a - t are taken directly from Table II,
# with thermochemistry from Table IV.
# -> Thermo needs to be reviewed, as deltaG for reactions are 
#    very important.
#
species(name = 'Csoot-*',
        atoms = 'H:0 C:1',
        thermo = const_cp(t0  = (1000., 'K'),
                          h0 = (51.7, 'kcal/mol'),
                          s0 = (19.5, 'cal/mol/K'),
                          cp0 = (8.41, 'cal/mol/K') ))

species(name = 'Csoot-H',
        atoms = 'H:1 C:1',
        thermo = const_cp(t0  = (1000., 'K'),
                          h0 = (11.4, 'kcal/mol'),
                          s0 = (21.0, 'cal/mol/K'),
                          cp0 = (8.41, 'cal/mol/K')) )	
#
# Forward rate constant taken from Frenklach/Wang:
surface_reaction( 'Csoot-H + H  => Csoot-* + H2',  [4.17E13, 0.0, 13.0])
surface_reaction( 'Csoot-* + H2 => Csoot-H + H',   [3.9E12, 0.0, 11.0])

surface_reaction( 'Csoot-H + OH  => Csoot-* + H2O',  [1.0E10, 0.734, 1.43])
surface_reaction( 'Csoot-* + H2O => Csoot-H + OH',   [3.68E8, 1.139, 17.1])

surface_reaction( 'Csoot-* + H => Csoot-H',   [2.0E13, 0.0, 0.0])

surface_reaction( 'Csoot-* + C2H2 => Csoot-H + H + 2 CB-CB3',   [8.0E7, 1.56, 3.8])

surface_reaction( 'Csoot-* + O2 + 2 CB-CB3 => Csoot-* + 2 CO',   [2.2E12, 0.00, 7.5])

#surface_reaction( 'OH + Csoot-H + CB-CB3 => Csoot-* + CO + H2',  [3.01577E10, 0.5, 0.0])
surface_reaction( 'OH + Csoot-H + CB-CB3 => Csoot-* + CO + H2',  stick(0.13, 0.0, 0.0))

