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rSPECMICP SpecMiCP / ReactMiCP
adimensional_system.cpp
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/*-------------------------------------------------------------------------------
Copyright (c) 2014,2015 F. Georget <fabieng@princeton.edu>, Princeton University
All rights reserved.
Redistribution and use in source and binary forms, with or without modification,
are permitted provided that the following conditions are met:
1. Redistributions of source code must retain the above copyright notice, this
list of conditions and the following disclaimer.
2. Redistributions in binary form must reproduce the above copyright notice,
this list of conditions and the following disclaimer in the documentation and/or
other materials provided with the distribution.
3. Neither the name of the copyright holder nor the names of its contributors
may be used to endorse or promote products derived from this software without
specific prior written permission.
THIS SOFTWARE IS PROVIDED BY THE COPYRIGHT HOLDERS AND CONTRIBUTORS "AS IS" AND
ANY EXPRESS OR IMPLIED WARRANTIES, INCLUDING, BUT NOT LIMITED TO, THE IMPLIED
WARRANTIES OF MERCHANTABILITY AND FITNESS FOR A PARTICULAR PURPOSE ARE
DISCLAIMED. IN NO EVENT SHALL THE COPYRIGHT HOLDER OR CONTRIBUTORS BE LIABLE FOR
ANY DIRECT, INDIRECT, INCIDENTAL, SPECIAL, EXEMPLARY, OR CONSEQUENTIAL DAMAGES
(INCLUDING, BUT NOT LIMITED TO, PROCUREMENT OF SUBSTITUTE GOODS OR SERVICES;
LOSS OF USE, DATA, OR PROFITS; OR BUSINESS INTERRUPTION) HOWEVER CAUSED AND ON
ANY THEORY OF LIABILITY, WHETHER IN CONTRACT, STRICT LIABILITY, OR TORT
(INCLUDING NEGLIGENCE OR OTHERWISE) ARISING IN ANY WAY OUT OF THE USE OF THIS
SOFTWARE, EVEN IF ADVISED OF THE POSSIBILITY OF SUCH DAMAGE.
-----------------------------------------------------------------------------*/
#include <cmath>
#include "adimensional_system.hpp"
#include "../../utils/log.hpp"
#include "../../physics/constants.hpp"
#include "../../physics/laws.hpp"
#include "adimensional_system_solution.hpp"
#include <random>
#include <iostream>
// uncomment to activate the finite difference jacobian
// #define SPECMICP_DEBUG_EQUATION_FD_JACOBIAN
namespace
specmicp
{
//constexpr scalar_t log10f() const {return std::log(10.0);}
//constexpr scalar_t log10 = log10f();
static
const
scalar_t
log10
=
std
::
log
(
10.0
);
// Constructor
// ===========
// No previous solution
// --------------------
AdimensionalSystem
::
AdimensionalSystem
(
RawDatabasePtr
&
ptrdata
,
const
AdimensionalSystemConstraints
&
constraints
,
const
AdimensionalSystemOptions
&
options
,
const
units
::
UnitsSet
&
units_set
)
:
AdimemsionalSystemNumbering
(
ptrdata
),
OptionsHandler
<
AdimensionalSystemOptions
>
(
options
),
units
::
UnitBaseClass
(
units_set
),
m_inert_volume_fraction
(
constraints
.
inert_volume_fraction
),
m_second
(
ptrdata
),
m_equations
(
total_dofs
(),
ptrdata
)
{
specmicp_assert
(
ptrdata
->
is_valid
());
m_fixed_values
.
setZero
(
ptrdata
->
nb_component
()
+
1
);
number_eq
(
constraints
);
}
// Previous solution
// -----------------
AdimensionalSystem
::
AdimensionalSystem
(
RawDatabasePtr
&
ptrdata
,
const
AdimensionalSystemConstraints
&
constraints
,
const
AdimensionalSystemSolution
&
previous_solution
,
const
AdimensionalSystemOptions
&
options
,
const
units
::
UnitsSet
&
units_set
)
:
AdimemsionalSystemNumbering
(
ptrdata
),
OptionsHandler
<
AdimensionalSystemOptions
>
(
options
),
units
::
UnitBaseClass
(
units_set
),
m_inert_volume_fraction
(
constraints
.
inert_volume_fraction
),
m_second
(
previous_solution
),
m_equations
(
total_dofs
(),
ptrdata
)
{
specmicp_assert
(
ptrdata
->
is_valid
());
m_fixed_values
.
setZero
(
ptrdata
->
nb_component
()
+
1
);
number_eq
(
constraints
);
}
// Secondary variables constructor
// ===============================
// No previous solution
// --------------------
AdimensionalSystem
::
SecondaryVariables
::
SecondaryVariables
(
const
RawDatabasePtr
&
data
)
:
secondary_molalities
(
Vector
::
Zero
(
data
->
nb_aqueous
())),
loggamma
(
Vector
::
Zero
(
data
->
nb_component
()
+
data
->
nb_aqueous
())),
gas_fugacity
(
Vector
::
Zero
(
data
->
nb_gas
())),
gas_concentration
(
Vector
::
Zero
(
data
->
nb_gas
())),
sorbed_concentrations
(
Vector
::
Zero
(
data
->
nb_sorbed
()))
{}
// Previous solution
// -----------------
AdimensionalSystem
::
SecondaryVariables
::
SecondaryVariables
(
const
AdimensionalSystemSolution
&
previous_solution
)
:
secondary_molalities
(
previous_solution
.
secondary_molalities
),
loggamma
(
previous_solution
.
log_gamma
),
gas_fugacity
(
previous_solution
.
gas_fugacities
),
gas_concentration
(
Vector
::
Zero
(
previous_solution
.
gas_fugacities
.
rows
())),
sorbed_concentrations
(
previous_solution
.
sorbed_molalities
)
{}
// IdEquations constructor
// =======================
AdimensionalSystem
::
IdEquations
::
IdEquations
(
index_t
nb_dofs
,
const
RawDatabasePtr
&
data
)
:
ideq
(
nb_dofs
,
no_equation
),
component_equation_type
(
data
->
nb_component
()
+
1
,
no_equation
),
fixed_activity_species
(
data
->
nb_component
()
+
1
,
no_species
),
active_aqueous
(
data
->
nb_aqueous
(),
false
),
active_gas
(
data
->
nb_gas
(),
false
),
active_sorbed
(
data
->
nb_sorbed
())
{}
// Equation numbering
// ==================
// Note : this function also computes scaling factor that would be used in the computation
// ------
void
AdimensionalSystem
::
number_eq
(
const
AdimensionalSystemConstraints
&
constraints
)
{
index_t
neq
=
0
;
// Water
// =====
if
(
constraints
.
water_equation
!=
WaterEquationType
::
NoEquation
)
{
m_equations
.
type_equation
(
dof_water
())
=
static_cast
<
index_t
>
(
constraints
.
water_equation
);
if
(
constraints
.
water_equation
==
WaterEquationType
::
MassConservation
)
{
m_fixed_values
(
dof_water
())
=
constraints
.
total_concentrations
(
dof_water
());
if
(
constraints
.
water_partial_pressure
.
use_partial_pressure_model
)
{
m_equations
.
use_water_pressure_model
=
true
;
m_equations
.
water_pressure_model
=
constraints
.
water_partial_pressure
.
partial_pressure_model
;
}
}
m_equations
.
add_equation
(
dof_water
(),
&
neq
);
}
// Aqueous components
// ==================
number_eq_aqueous_component
(
constraints
,
neq
);
// Surface model
// =============
if
(
constraints
.
surface_model
.
model_type
==
SurfaceEquationType
::
Equilibrium
)
{
// add the equation
m_equations
.
add_equation
(
dof_surface
(),
&
neq
);
m_equations
.
type_equation
(
dof_surface
())
=
static_cast
<
index_t
>
(
constraints
.
surface_model
.
model_type
);
// setup the total concentration
m_fixed_values
(
dof_surface
())
=
constraints
.
surface_model
.
concentration
;
}
// Secondary species
// =================
// Secondary aqueous species
// -------------------------
bool
include_half_cell_reaction
=
(
constraints
.
electron_constraint
.
equation_type
!=
ElectronEquationType
::
NoEquation
);
bool
solve_electron_equation
{
false
};
for
(
auto
j:
m_data
->
range_aqueous
())
{
bool
can_exist
{
true
};
if
(
include_half_cell_reaction
or
not
m_data
->
is_half_cell_reaction
(
j
))
for
(
const
auto
&
k:
m_equations
.
nonactive_component
)
{
if
(
m_data
->
nu_aqueous
(
j
,
k
)
!=
0.0
)
{
can_exist
=
false
;
break
;
}
}
else
{
can_exist
=
false
;
}
m_equations
.
set_aqueous_active
(
j
,
can_exist
);
if
(
can_exist
and
m_data
->
is_half_cell_reaction
(
j
))
solve_electron_equation
=
true
;
//std::cout << m_data->labels_aqueous[j] << "can exist ? " << can_exist << " - logk : " << m_data->logk_aqueous(j) << std::endl;
}
// Gas
// ---
for
(
index_t
k:
m_data
->
range_gas
())
{
bool
can_exist
=
true
;
for
(
const
index_t
&
n:
m_equations
.
nonactive_component
)
{
if
(
m_data
->
nu_gas
(
k
,
n
)
!=
0.0
)
{
can_exist
=
false
;
break
;
}
}
m_equations
.
set_gas_active
(
k
,
can_exist
);
}
// Unit scaling for the gaseous total concentration
switch
(
get_units
().
length
)
{
case
units
::
LengthUnit
::
decimeter:
m_scaling_gas
=
1e-3
;
break
;
case
units
::
LengthUnit
::
centimeter:
m_scaling_gas
=
1e-6
;
break
;
default
:
m_scaling_gas
=
1.0
;
break
;
}
// Sorbed species
// --------------
for
(
index_t
s:
m_data
->
range_sorbed
())
{
// Check if the surface model is computed
if
(
constraints
.
surface_model
.
model_type
!=
SurfaceEquationType
::
Equilibrium
)
{
m_equations
.
set_sorbed_active
(
s
,
false
);
continue
;
}
// If so, check that all components of the sorbed species exist
bool
can_exist
=
true
;
for
(
const
index_t
&
k:
m_equations
.
nonactive_component
)
{
if
(
m_data
->
nu_sorbed
(
s
,
k
)
!=
0.0
)
{
can_exist
=
false
;
break
;
}
}
m_equations
.
set_sorbed_active
(
s
,
can_exist
);
}
// Electron equation
// -----------------
if
(
solve_electron_equation
)
{
m_equations
.
add_equation
(
dof_electron
(),
&
neq
);
m_equations
.
type_equation
(
dof_electron
())
=
static_cast
<
index_t
>
(
constraints
.
electron_constraint
.
equation_type
);
if
(
constraints
.
electron_constraint
.
equation_type
==
ElectronEquationType
::
Equilibrium
)
{
m_fixed_values
(
dof_electron
())
=
0.0
;
}
else
if
(
constraints
.
electron_constraint
.
equation_type
==
ElectronEquationType
::
FixedpE
)
{
m_fixed_values
(
dof_electron
())
=
constraints
.
electron_constraint
.
fixed_value
;
m_equations
.
related_species
(
dof_electron
())
=
constraints
.
electron_constraint
.
species
;
//assert(m_fixed_activity_species[dof_electron()] >= 0
// and m_fixed_activity_species[dof_electron()] < m_data->nb_aqueous());
//assert(m_data->is_half_cell_reaction(m_fixed_activity_species[dof_electron()]));
}
// scaling
if
(
get_options
().
scaling_electron
==
0.0
)
{
for
(
index_t
component
:
m_data
->
range_aqueous_component
())
{
if
(
aqueous_component_equation_type
(
component
)
==
AqueousComponentEquationType
::
MassConservation
)
{
get_options
().
scaling_electron
=
total_concentration_bc
(
component
);
break
;
}
}
}
}
// above equations are 'free' (i.e. non constrained)
m_equations
.
nb_free_variables
=
neq
;
// following equations are complementarity conditions
// Minerals
// ========
m_scaling_molar_volume
=
m_data
->
scaling_molar_volume
(
get_units
().
length
);
for
(
index_t
m:
m_data
->
range_mineral
())
{
bool
can_precipitate
=
true
;
// just check that the molar volume exist
auto
molar_volume
=
m_data
->
molar_volume_mineral
(
m
);
// Remove minerals that cannot precipitate
for
(
index_t
&
k:
m_equations
.
nonactive_component
)
{
if
(
m_data
->
nu_mineral
(
m
,
k
)
!=
0.0
and
molar_volume
>
0.0
)
{
can_precipitate
=
false
;
break
;
// this is not a mineral that can precipitate
}
}
if
(
can_precipitate
)
{
m_equations
.
add_equation
(
dof_mineral
(
m
),
&
neq
);
}
}
m_equations
.
nb_tot_variables
=
neq
;
m_equations
.
nb_complementarity_variables
=
m_equations
.
nb_tot_variables
-
m_equations
.
nb_free_variables
;
}
void
AdimensionalSystem
::
number_eq_aqueous_component
(
const
AdimensionalSystemConstraints
&
constraints
,
index_t
&
neq
)
{
using
EqT
=
AqueousComponentEquationType
;
// First set the charge keeper
if
(
constraints
.
charge_keeper
!=
no_species
)
{
if
(
constraints
.
charge_keeper
==
0
or
constraints
.
charge_keeper
>
m_data
->
nb_component
())
{
throw
std
::
invalid_argument
(
"The charge keeper must be an aqueous component. Invalid argument : "
+
std
::
to_string
(
constraints
.
charge_keeper
));
}
m_equations
.
type_equation
(
dof_component
(
constraints
.
charge_keeper
))
=
static_cast
<
index_t
>
(
EqT
::
ChargeBalance
);
}
// Then go over fix fugacity gas
for
(
const
auto
&
it:
constraints
.
fixed_fugacity_cs
)
{
if
(
m_equations
.
type_equation
(
dof_component
(
it
.
id_component
))
!=
static_cast
<
index_t
>
(
EqT
::
NoEquation
))
{
throw
std
::
invalid_argument
(
"Component '"
+
m_data
->
components
.
get_label
(
it
.
id_component
)
+
"' is already constrained, a fixed fugacity condition can not be applied"
);
}
m_equations
.
type_equation
(
dof_component
(
it
.
id_component
))
=
static_cast
<
int
>
(
EqT
::
FixedFugacity
);
m_fixed_values
(
it
.
id_component
)
=
it
.
log_value
;
m_equations
.
related_species
(
it
.
id_component
)
=
it
.
id_gas
;
}
// Then over the fixed activity species
for
(
const
auto
&
it:
constraints
.
fixed_activity_cs
)
{
if
(
m_equations
.
type_equation
(
dof_component
(
it
.
id_component
))
!=
static_cast
<
index_t
>
(
EqT
::
NoEquation
))
{
throw
std
::
invalid_argument
(
"Component '"
+
m_data
->
components
.
get_label
(
it
.
id_component
)
+
"' is already constrained, a fixed activity condition can not be applied."
);
}
m_equations
.
type_equation
(
dof_component
(
it
.
id_component
))
=
static_cast
<
index_t
>
(
EqT
::
FixedActivity
);
m_fixed_values
(
it
.
id_component
)
=
it
.
log_value
;
}
// Then the fixed molality components
for
(
const
auto
&
it:
constraints
.
fixed_molality_cs
)
{
if
(
m_equations
.
type_equation
(
dof_component
(
it
.
id_component
))
!=
static_cast
<
index_t
>
(
EqT
::
NoEquation
))
{
throw
std
::
invalid_argument
(
"Component '"
+
m_data
->
components
.
get_label
(
it
.
id_component
)
+
"' is already constrained, a fixed molality condition can not be applied."
);
}
m_equations
.
type_equation
(
dof_component
(
it
.
id_component
))
=
static_cast
<
index_t
>
(
EqT
::
FixedMolality
);
m_fixed_values
(
it
.
id_component
)
=
it
.
log_value
;
}
// Finally number the equations
for
(
index_t
component:
m_data
->
range_aqueous_component
())
{
// If no equation is assigned yet
if
(
m_equations
.
type_equation
(
dof_component
(
component
))
==
static_cast
<
index_t
>
(
EqT
::
NoEquation
))
{
// Mass is conserved for this component
//###FIXME: H[+], HO[-]
const
scalar_t
&
total_concentration
=
constraints
.
total_concentrations
(
dof_component
(
component
));
if
(
std
::
abs
(
total_concentration
)
>
get_options
().
cutoff_total_concentration
)
{
m_equations
.
type_equation
(
dof_component
(
component
))
=
static_cast
<
index_t
>
(
EqT
::
MassConservation
);
m_fixed_values
(
dof_component
(
component
))
=
total_concentration
;
m_equations
.
add_equation
(
component
,
&
neq
);
}
else
// add component to the nonactive component list
{
m_equations
.
add_non_active_component
(
component
);
}
}
// If equation is already assigned
else
{
m_equations
.
add_equation
(
component
,
&
neq
);
}
}
if
(
stdlog
::
ReportLevel
()
>=
logger
::
Debug
and
m_equations
.
nonactive_component
.
size
()
>
0
)
{
// if in debug mode list the non active components
DEBUG
<<
"Non active components :"
;
for
(
auto
it:
m_equations
.
nonactive_component
)
{
DEBUG
<<
" - "
<<
it
;
}
}
}
// ================ //
// //
// Residuals //
// //
// ================ //
scalar_t
AdimensionalSystem
::
weigthed_sum_aqueous
(
index_t
component
)
const
{
scalar_t
sum
=
0.0
;
for
(
index_t
aqueous:
m_data
->
range_aqueous
())
{
if
(
not
is_aqueous_active
(
aqueous
))
continue
;
sum
+=
m_data
->
nu_aqueous
(
aqueous
,
component
)
*
secondary_molality
(
aqueous
);
}
return
sum
;
}
scalar_t
AdimensionalSystem
::
diff_weigthed_sum_aqueous
(
index_t
diff_component
,
index_t
component
)
const
{
scalar_t
sum
=
0.0
;
for
(
index_t
aqueous:
m_data
->
range_aqueous
())
{
if
(
not
is_aqueous_active
(
aqueous
))
continue
;
sum
+=
log10
*
m_data
->
nu_aqueous
(
aqueous
,
diff_component
)
*
m_data
->
nu_aqueous
(
aqueous
,
component
)
*
secondary_molality
(
aqueous
);
}
return
sum
;
}
scalar_t
AdimensionalSystem
::
weigthed_sum_sorbed
(
index_t
component
)
const
{
scalar_t
sum
=
0.0
;
for
(
index_t
s:
m_data
->
range_sorbed
())
{
if
(
not
is_active_sorbed
(
s
))
continue
;
sum
+=
m_data
->
nu_sorbed
(
s
,
component
)
*
sorbed_species_concentration
(
s
);
}
return
sum
;
}
scalar_t
AdimensionalSystem
::
diff_weigthed_sum_sorbed
(
index_t
diff_component
,
index_t
component
)
const
{
scalar_t
sum
=
0.0
;
for
(
index_t
s:
m_data
->
range_sorbed
())
{
if
(
not
is_active_sorbed
(
s
))
continue
;
sum
+=
log10
*
m_data
->
nu_sorbed
(
s
,
diff_component
)
*
m_data
->
nu_sorbed
(
s
,
component
)
*
sorbed_species_concentration
(
s
);
}
return
sum
;
}
scalar_t
AdimensionalSystem
::
diff_surface_weigthed_sum_sorbed
(
index_t
component
)
const
{
scalar_t
sum
=
0.0
;
for
(
index_t
s:
m_data
->
range_sorbed
())
{
if
(
not
is_active_sorbed
(
s
))
continue
;
sum
+=
log10
*
m_data
->
nb_sorption_sites
(
s
)
*
m_data
->
nu_sorbed
(
s
,
component
)
*
sorbed_species_concentration
(
s
);
}
return
sum
;
}
scalar_t
AdimensionalSystem
::
weigthed_sum_mineral
(
const
Vector
&
x
,
index_t
component
)
const
{
scalar_t
sum
=
0.0
;
for
(
index_t
m:
m_data
->
range_mineral
())
{
if
(
ideq_min
(
m
)
==
no_equation
or
m_data
->
nu_mineral
(
m
,
component
)
==
0.0
)
continue
;
const
auto
concentration
=
saturation_mineral
(
x
,
m
)
/
molar_volume_mineral
(
m
);
sum
+=
m_data
->
nu_mineral
(
m
,
component
)
*
concentration
;
}
return
sum
;
}
scalar_t
AdimensionalSystem
::
weigthed_sum_gas
(
index_t
component
)
const
{
scalar_t
sum
=
0.0
;
for
(
index_t
k:
m_data
->
range_gas
())
{
if
(
not
is_active_gas
(
k
)
or
m_data
->
nu_gas
(
k
,
component
)
==
0.0
)
continue
;
sum
+=
m_data
->
nu_gas
(
k
,
component
)
*
gas_concentration
(
k
);
}
return
sum
;
}
scalar_t
AdimensionalSystem
::
diff_weigthed_sum_gas
(
index_t
diff_component
,
index_t
component
)
const
{
scalar_t
sum
=
0.0
;
for
(
index_t
k:
m_data
->
range_gas
())
{
if
(
not
is_active_gas
(
k
)
or
m_data
->
nu_gas
(
k
,
component
)
==
0.0
)
continue
;
sum
+=
log10
*
m_data
->
nu_gas
(
k
,
diff_component
)
*
m_data
->
nu_gas
(
k
,
component
)
*
gas_concentration
(
k
);
}
return
sum
;
}
scalar_t
AdimensionalSystem
::
residual_water
(
const
Vector
&
x
)
const
{
scalar_t
res
{
0.0
};
if
(
water_equation_type
()
==
WaterEquationType
::
MassConservation
)
{
const
scalar_t
conc_w
=
density_water
()
*
saturation_water
(
x
);
res
=
total_concentration_bc
(
0
);
res
-=
conc_w
/
m_data
->
molar_mass_basis
(
0
);
res
-=
conc_w
*
weigthed_sum_aqueous
(
0
);
if
(
ideq_surf
()
!=
no_equation
)
res
-=
conc_w
*
weigthed_sum_sorbed
(
0
);
res
-=
weigthed_sum_mineral
(
x
,
0
);
if
(
m_data
->
nb_gas
()
>
0
)
res
-=
weigthed_sum_gas
(
0
);
if
(
m_equations
.
use_water_pressure_model
)
{
const
scalar_t
porosity
=
m_second
.
porosity
;
scalar_t
sat_w
=
saturation_water
(
x
)
/
porosity
;
if
(
sat_w
<
1
)
{
const
scalar_t
pressure
=
m_equations
.
water_pressure_model
(
sat_w
);
res
-=
m_scaling_gas
*
(
porosity
-
saturation_water
(
x
))
*
(
pressure
/
(
constants
::
gas_constant
*
temperature
()));
}
}
res
/=
total_concentration_bc
(
0
);
}
else
if
(
water_equation_type
()
==
WaterEquationType
::
SaturatedSystem
)
{
res
=
1
-
saturation_water
(
x
)
-
m_inert_volume_fraction
;
for
(
index_t
mineral:
m_data
->
range_mineral
())
{
res
-=
saturation_mineral
(
x
,
mineral
);
}
}
return
res
;
}
scalar_t
AdimensionalSystem
::
residual_component
(
const
Vector
&
x
,
index_t
component
)
const
{
specmicp_assert
(
aqueous_component_equation_type
(
component
)
==
AqueousComponentEquationType
::
MassConservation
);
const
scalar_t
conc_w
=
density_water
()
*
saturation_water
(
x
);
scalar_t
res
=
total_concentration_bc
(
component
);
res
-=
conc_w
*
component_molality
(
x
,
component
);
res
-=
conc_w
*
weigthed_sum_aqueous
(
component
);
if
(
ideq_surf
()
!=
no_equation
)
res
-=
conc_w
*
weigthed_sum_sorbed
(
component
);
res
-=
weigthed_sum_mineral
(
x
,
component
);
if
(
m_data
->
nb_gas
()
>
0
)
res
-=
weigthed_sum_gas
(
component
);
res
/=
total_concentration_bc
(
component
);
return
res
;
}
scalar_t
AdimensionalSystem
::
residual_fixed_activity
(
const
Vector
&
x
,
index_t
component
)
const
{
specmicp_assert
(
aqueous_component_equation_type
(
component
)
==
AqueousComponentEquationType
::
FixedActivity
);
scalar_t
res
=
(
fixed_activity_bc
(
component
)
-
log_gamma_component
(
component
)
-
log_component_molality
(
x
,
component
)
);
res
/=
fixed_activity_bc
(
component
);
return
res
;
}
scalar_t
AdimensionalSystem
::
residual_fixed_molality
(
const
Vector
&
x
,
index_t
component
)
const
{
specmicp_assert
(
aqueous_component_equation_type
(
component
)
==
AqueousComponentEquationType
::
FixedMolality
);
scalar_t
res
=
(
fixed_molality_bc
(
component
)
-
log_component_molality
(
x
,
component
)
);
res
/=
fixed_molality_bc
(
component
);
return
res
;
}
scalar_t
AdimensionalSystem
::
residual_fixed_fugacity
(
const
Vector
&
x
,
index_t
component
)
const
{
specmicp_assert
(
aqueous_component_equation_type
(
component
)
==
AqueousComponentEquationType
::
FixedFugacity
);
index_t
id_g
=
m_equations
.
fixed_activity_species
[
component
];
scalar_t
res
=
fixed_fugacity_bc
(
component
)
+
m_data
->
logk_gas
(
id_g
);
for
(
index_t
component:
m_data
->
range_aqueous_component
())
{
if
(
m_data
->
nu_gas
(
id_g
,
component
)
==
0
)
continue
;
res
-=
m_data
->
nu_gas
(
id_g
,
component
)
*
(
log_gamma_component
(
component
)
+
log_component_molality
(
x
,
component
));
}
res
/=
fixed_fugacity_bc
(
component
);
return
res
;
}
scalar_t
AdimensionalSystem
::
residual_mineral
(
const
Vector
&
x
,
index_t
m
)
const
{
specmicp_assert
(
ideq_min
(
m
)
!=
no_equation
);
scalar_t
res
=
m_data
->
logk_mineral
(
m
);
for
(
index_t
i:
m_data
->
range_aqueous_component
())
{
if
(
m_data
->
nu_mineral
(
m
,
i
)
!=
0
)
{
const
auto
log_activity_i
=
log_component_molality
(
x
,
i
)
+
log_gamma_component
(
i
);
res
-=
m_data
->
nu_mineral
(
m
,
i
)
*
log_activity_i
;
}
}
if
(
ideq_electron
()
!=
no_equation
and
m_data
->
is_mineral_half_cell_reaction
(
m
))
res
-=
m_data
->
nu_mineral
(
m
,
m_data
->
electron_index
())
*
log_activity_electron
(
x
);
return
res
;
}
scalar_t
AdimensionalSystem
::
residual_charge_conservation
(
const
Vector
&
x
)
const
{
scalar_t
res
=
0.0
;
for
(
index_t
i:
m_data
->
range_aqueous_component
())
{
if
(
m_data
->
charge_component
(
i
)
!=
0
and
ideq_paq
(
i
)
!=
no_equation
)
res
+=
m_data
->
charge_component
(
i
)
*
component_molality
(
x
,
i
);
}
for
(
index_t
j:
m_data
->
range_aqueous
())
{
if
(
m_data
->
charge_aqueous
(
j
)
==
0
and
not
is_aqueous_active
(
j
))
continue
;
res
+=
m_data
->
charge_aqueous
(
j
)
*
secondary_molality
(
j
);
}
return
res
;
}
scalar_t
AdimensionalSystem
::
residual_surface
(
const
Vector
&
x
)
const
{
specmicp_assert
(
ideq_surf
()
!=
no_equation
);
const
scalar_t
conc_w
=
density_water
()
*
saturation_water
(
x
);
scalar_t
res
=
surface_total_concentration
()
-
conc_w
*
free_sorption_site_concentration
(
x
);
for
(
index_t
s:
m_data
->
range_sorbed
())
{
if
(
not
is_active_sorbed
(
s
))
continue
;
res
-=
conc_w
*
m_data
->
nb_sorption_sites
(
s
)
*
sorbed_species_concentration
(
s
);
}
return
res
/
surface_total_concentration
();
}
scalar_t
AdimensionalSystem
::
residual_electron
(
const
Vector
&
x
)
const
{
specmicp_assert
(
electron_equation_type
()
==
ElectronEquationType
::
Equilibrium
);
const
scalar_t
conc_w
=
density_water
()
*
saturation_water
(
x
);
scalar_t
res
=
0.0
;
res
-=
conc_w
*
weigthed_sum_aqueous
(
m_data
->
electron_index
());
if
(
ideq_surf
()
!=
no_equation
)
res
-=
conc_w
*
weigthed_sum_sorbed
(
m_data
->
electron_index
());
res
-=
weigthed_sum_mineral
(
x
,
m_data
->
electron_index
());
if
(
m_data
->
nb_gas
()
>
0
)
res
-=
weigthed_sum_gas
(
m_data
->
electron_index
());
return
res
/
get_options
().
scaling_electron
;
}
void
AdimensionalSystem
::
get_residuals
(
const
Vector
&
x
,
Vector
&
residual
)
{
residual
.
resize
(
total_variables
());
// initialisation of 'main' secondary variables
// They are especially nessary if the finite difference jacobian is used
// and for the linesearch
m_second
.
porosity
=
1
-
sum_saturation_minerals
(
x
);
m_second
.
saturation_gas
=
m_second
.
porosity
-
saturation_water
(
x
);
set_secondary_concentration
(
x
);
set_sorbed_concentrations
(
x
);
//
// water
if
(
ideq_w
()
!=
no_equation
)
residual
(
ideq_w
())
=
residual_water
(
x
);
// aqueous component
for
(
index_t
i:
m_data
->
range_aqueous_component
())
{
switch
(
aqueous_component_equation_type
(
i
))
{
case
AqueousComponentEquationType
::
NoEquation:
break
;
case
AqueousComponentEquationType
::
MassConservation:
residual
(
ideq_paq
(
i
))
=
residual_component
(
x
,
i
);
break
;
case
AqueousComponentEquationType
::
ChargeBalance:
residual
(
ideq_paq
(
i
))
=
residual_charge_conservation
(
x
);
break
;
case
AqueousComponentEquationType
::
FixedActivity:
residual
(
ideq_paq
(
i
))
=
residual_fixed_activity
(
x
,
i
);
break
;
case
AqueousComponentEquationType
::
FixedFugacity:
residual
(
ideq_paq
(
i
))
=
residual_fixed_fugacity
(
x
,
i
);
break
;
case
AqueousComponentEquationType
::
FixedMolality:
residual
(
ideq_paq
(
i
))
=
residual_fixed_molality
(
x
,
i
);
break
;
}
}
// surface
if
(
ideq_surf
()
!=
no_equation
)
residual
(
ideq_surf
())
=
residual_surface
(
x
);
// mineral
for
(
index_t
m:
m_data
->
range_mineral
())
{
if
(
ideq_min
(
m
)
!=
no_equation
)
residual
(
ideq_min
(
m
))
=
residual_mineral
(
x
,
m
);
}
// electron
if
(
ideq_electron
()
!=
no_equation
)
residual
(
ideq_electron
())
=
residual_electron
(
x
);
// std::cout << residual << std::endl;
}
// ================ //
// //
// Jacobian //
// //
// ================ //
void
AdimensionalSystem
::
get_jacobian
(
Vector
&
x
,
Matrix
&
jacobian
)
// //non-optimized Finite difference, for test only
#ifdef SPECMICP_DEBUG_EQUATION_FD_JACOBIAN
{
finite_difference_jacobian
(
x
,
jacobian
);
return
;
}
#else
// analytical jacobian
{
analytical_jacobian
(
x
,
jacobian
);
return
;
}
#endif
void
AdimensionalSystem
::
finite_difference_jacobian
(
Vector
&
x
,
Matrix
&
jacobian
)
{
const
int
neq
=
total_variables
();
Eigen
::
VectorXd
res
(
neq
);
Eigen
::
VectorXd
perturbed_res
(
neq
);
jacobian
.
setZero
(
neq
,
neq
);
get_residuals
(
x
,
res
);
for
(
int
j
=
0
;
j
<
neq
;
++
j
)
{
double
h
=
1e-8
*
std
::
abs
(
x
(
j
));
if
(
h
==
0
)
h
=
1e-8
;
double
tmp
=
x
(
j
);
x
(
j
)
+=
h
;
h
=
x
(
j
)
-
tmp
;
get_residuals
(
x
,
perturbed_res
);
for
(
int
i
=
0
;
i
<
neq
;
++
i
)
{
jacobian
(
i
,
j
)
=
(
perturbed_res
(
i
)
-
res
(
i
))
/
h
;
}
x
(
j
)
=
tmp
;
}
}
void
AdimensionalSystem
::
analytical_jacobian
(
Vector
&
x
,
Matrix
&
jacobian
)
{
const
int
neq
=
total_variables
();
jacobian
.
setZero
(
neq
,
neq
);
// water
jacobian_water
(
x
,
jacobian
);
// aqueous component
jacobian_aqueous_components
(
x
,
jacobian
);
// surface
if
(
ideq_surf
()
!=
no_equation
)
jacobian_surface
(
x
,
jacobian
);
// mineral equilibrium
jacobian_minerals
(
x
,
jacobian
);
// electron
if
(
ideq_electron
()
!=
no_equation
)
jacobian_electron
(
x
,
jacobian
);
}
void
AdimensionalSystem
::
jacobian_water
(
Vector
&
x
,
Matrix
&
jacobian
)
{
if
(
water_equation_type
()
==
WaterEquationType
::
MassConservation
)
{
const
index_t
idw
=
ideq_w
();
const
scalar_t
rho_w
=
density_water
();
const
scalar_t
factor
=
total_concentration_bc
(
0
);
scalar_t
tmp
=
-
1.0
/
m_data
->
molar_mass_basis
(
0
);
tmp
-=
weigthed_sum_aqueous
(
0
);
tmp
-=
weigthed_sum_sorbed
(
0
);
tmp
*=
rho_w
;
tmp
-=
-
weigthed_sum_gas
(
0
);
if
(
m_equations
.
use_water_pressure_model
)
{
const
scalar_t
porosity
=
(
1
-
sum_saturation_minerals
(
x
)
-
m_inert_volume_fraction
);
const
scalar_t
sat_w
=
saturation_water
(
x
)
/
porosity
;
if
(
sat_w
<
1
)
// TODO bound checking
{
scalar_t
sp
=
sat_w
*
(
1.0
+
eps_jacobian
);
if
(
sp
==
0.0
)
sp
=
eps_jacobian
;
const
scalar_t
h
=
sp
-
sat_w
;
const
scalar_t
pv_sds
=
m_equations
.
water_pressure_model
(
sp
);
const
scalar_t
pv_s
=
m_equations
.
water_pressure_model
(
sat_w
);
const
scalar_t
diff
=
(
pv_sds
-
pv_s
)
/
h
;
tmp
-=
m_scaling_gas
/
(
constants
::
gas_constant
*
temperature
())
*
(
(
1
-
sat_w
)
*
diff
-
pv_s
);
}
}
jacobian
(
idw
,
idw
)
=
tmp
/
factor
;
const
scalar_t
conc_w
=
density_water
()
*
saturation_water
(
x
);
for
(
index_t
k:
m_data
->
range_aqueous_component
())
{
if
(
ideq_paq
(
k
)
==
no_equation
)
continue
;
scalar_t
tmp
=
0.0
;
tmp
-=
diff_weigthed_sum_aqueous
(
k
,
0
);
tmp
-=
diff_weigthed_sum_sorbed
(
k
,
0
);
// fixme gas
tmp
*=
conc_w
;
tmp
-=
diff_weigthed_sum_gas
(
k
,
0
);
jacobian
(
idw
,
ideq_paq
(
k
))
=
tmp
/
factor
;
}
if
(
ideq_electron
()
!=
no_equation
)
{
scalar_t
tmp
=
0.0
;
tmp
-=
diff_weigthed_sum_aqueous
(
m_data
->
electron_index
(),
0
);
tmp
-=
diff_weigthed_sum_sorbed
(
m_data
->
electron_index
(),
0
);
tmp
*=
conc_w
;
tmp
-=
diff_weigthed_sum_gas
(
m_data
->
electron_index
(),
0
);
jacobian
(
idw
,
ideq_electron
())
=
tmp
/
factor
;
}
for
(
index_t
m:
m_data
->
range_mineral
())
{
if
(
ideq_min
(
m
)
==
no_equation
)
continue
;
jacobian
(
idw
,
ideq_min
(
m
))
=
-
m_data
->
nu_mineral
(
m
,
0
)
/
molar_volume_mineral
(
m
)
/
factor
;
}
}
else
if
(
water_equation_type
()
==
WaterEquationType
::
SaturatedSystem
)
{
const
index_t
idw
=
ideq_w
();
jacobian
(
idw
,
idw
)
=
-
1
;
for
(
index_t
m:
m_data
->
range_mineral
())
{
if
(
ideq_min
(
m
)
==
no_equation
)
continue
;
jacobian
(
idw
,
ideq_min
(
m
))
=
-
1
;
}
}
}
void
AdimensionalSystem
::
jacobian_aqueous_components
(
Vector
&
x
,
Matrix
&
jacobian
)
{
for
(
index_t
i:
m_data
->
range_aqueous_component
())
{
const
index_t
idp
=
ideq_paq
(
i
);
if
(
idp
==
no_equation
)
continue
;
switch
(
aqueous_component_equation_type
(
i
))
{
case
AqueousComponentEquationType
::
NoEquation:
continue
;
// Mass balance equation
// =====================
case
AqueousComponentEquationType
::
MassConservation:
{
const
scalar_t
conc_w
=
density_water
()
*
saturation_water
(
x
);
const
scalar_t
factor
=
total_concentration_bc
(
i
);
// Aqueous components
for
(
index_t
k:
m_data
->
range_aqueous_component
())
{
if
(
ideq_paq
(
k
)
==
no_equation
)
continue
;
scalar_t
tmp_iip
=
0
;
if
(
k
==
i
)
tmp_iip
-=
component_molality
(
x
,
i
)
*
log10
;
tmp_iip
-=
diff_weigthed_sum_aqueous
(
k
,
i
);
tmp_iip
-=
diff_weigthed_sum_sorbed
(
k
,
i
);
tmp_iip
*=
conc_w
;
tmp_iip
-=
diff_weigthed_sum_gas
(
k
,
i
);
jacobian
(
idp
,
ideq_paq
(
k
))
=
tmp_iip
/
factor
;
}
// Minerals
for
(
index_t
m:
m_data
->
range_mineral
())
{
if
(
ideq_min
(
m
)
==
no_equation
)
continue
;
jacobian
(
idp
,
ideq_min
(
m
))
=
-
m_data
->
nu_mineral
(
m
,
i
)
/
molar_volume_mineral
(
m
)
/
factor
;
}
// Water
if
(
ideq_w
()
!=
no_equation
)
{
scalar_t
tmp_iw
=
-
component_molality
(
x
,
i
);
tmp_iw
-=
weigthed_sum_aqueous
(
i
);
tmp_iw
-=
weigthed_sum_sorbed
(
i
);
tmp_iw
*=
density_water
();
jacobian
(
idp
,
ideq_w
())
=
tmp_iw
/
factor
;
}
// Surface
if
(
ideq_surf
()
!=
no_equation
)
{
scalar_t
tmp_s
=
-
conc_w
*
diff_surface_weigthed_sum_sorbed
(
i
);
jacobian
(
idp
,
ideq_surf
())
=
tmp_s
/
factor
;
}
// Electron
if
(
ideq_electron
()
!=
no_equation
)
{
scalar_t
tmp
=
0.0
;
tmp
-=
diff_weigthed_sum_aqueous
(
m_data
->
electron_index
(),
i
);
tmp
-=
diff_weigthed_sum_sorbed
(
m_data
->
electron_index
(),
i
);
tmp
*=
conc_w
;
tmp
-=
diff_weigthed_sum_gas
(
m_data
->
electron_index
(),
i
);
jacobian
(
idp
,
ideq_electron
())
=
tmp
/
factor
;
}
break
;
}
// Charge balance equation
// =======================
case
AqueousComponentEquationType
::
ChargeBalance:
{
// Aqueous components
for
(
index_t
k:
m_data
->
range_aqueous_component
())
{
const
index_t
idc
=
ideq_paq
(
k
);
if
(
idc
==
no_equation
)
continue
;
scalar_t
tmp_drdb
=
0.0
;
if
(
m_data
->
charge_component
(
k
)
!=
0.0
)
tmp_drdb
=
m_data
->
charge_component
(
k
);
// Secondary species
for
(
index_t
j:
m_data
->
range_aqueous
())
{
if
(
not
is_aqueous_active
(
j
)
or
m_data
->
nu_aqueous
(
j
,
k
)
==
0.0
or
m_data
->
charge_aqueous
(
j
)
==
0.0
)
continue
;
scalar_t
tmp_value
=
m_data
->
nu_aqueous
(
j
,
k
)
*
m_data
->
charge_aqueous
(
j
);
tmp_value
*=
secondary_molality
(
j
)
/
component_molality
(
x
,
k
);
tmp_drdb
+=
tmp_value
;
}
jacobian
(
idp
,
idc
)
+=
component_molality
(
x
,
k
)
*
log10
*
tmp_drdb
;
}
break
;
}
// Fixed activity equation
// =======================
case
AqueousComponentEquationType
::
FixedActivity:
{
jacobian
(
idp
,
idp
)
=
-
1.0
/
fixed_activity_bc
(
i
);
break
;
}
// Fixed fugacity equation
// =======================
case
AqueousComponentEquationType
::
FixedFugacity:
{
index_t
id_g
=
m_equations
.
fixed_activity_species
[
i
];
for
(
index_t
k:
m_data
->
range_aqueous_component
())
{
if
(
ideq_paq
(
k
)
==
no_equation
or
m_data
->
nu_gas
(
id_g
,
k
)
==
0.0
)
continue
;
jacobian
(
idp
,
ideq_paq
(
k
))
=
-
m_data
->
nu_gas
(
id_g
,
k
)
/
fixed_fugacity_bc
(
i
);
}
break
;
}
// end case
// Fixed molality component
// ========================
case
AqueousComponentEquationType
::
FixedMolality:
{
jacobian
(
idp
,
idp
)
=
-
1.0
/
fixed_molality_bc
(
i
);
break
;
}
}
// end switch
}
}
void
AdimensionalSystem
::
jacobian_minerals
(
Vector
&
x
,
Matrix
&
jacobian
)
{
for
(
index_t
m:
m_data
->
range_mineral
())
{
const
index_t
idm
=
ideq_min
(
m
);
if
(
idm
==
no_equation
)
continue
;
for
(
index_t
i:
m_data
->
range_aqueous_component
())
{
if
(
ideq_paq
(
i
)
==
no_equation
)
continue
;
jacobian
(
idm
,
ideq_paq
(
i
))
=
-
m_data
->
nu_mineral
(
m
,
i
);
}
if
(
ideq_electron
()
!=
no_equation
and
m_data
->
is_mineral_half_cell_reaction
(
m
))
jacobian
(
idm
,
ideq_electron
())
=
-
m_data
->
nu_mineral
(
m
,
m_data
->
electron_index
());
}
}
void
AdimensionalSystem
::
jacobian_surface
(
Vector
&
x
,
Matrix
&
jacobian
)
{
const
index_t
ids
=
ideq_surf
();
const
scalar_t
factor
=
surface_total_concentration
();
const
scalar_t
conc_w
=
density_water
()
*
saturation_water
(
x
);
specmicp_assert
(
ids
!=
no_equation
);
scalar_t
tmp_s
=
-
free_sorption_site_concentration
(
x
);
for
(
index_t
s:
m_data
->
range_sorbed
())
{
if
(
not
is_active_sorbed
(
s
))
continue
;
tmp_s
-=
m_data
->
nb_sorption_sites
(
s
)
*
m_data
->
nb_sorption_sites
(
s
)
*
sorbed_species_concentration
(
s
);
}
jacobian
(
ids
,
ids
)
=
conc_w
*
log10
*
tmp_s
/
factor
;
// water
const
index_t
idw
=
ideq_w
();
if
(
idw
!=
no_equation
)
{
const
scalar_t
rho_w
=
density_water
();
scalar_t
tmp_w
=
-
free_sorption_site_concentration
(
x
);
for
(
index_t
s:
m_data
->
range_sorbed
())
{
if
(
not
is_active_sorbed
(
s
))
continue
;
tmp_w
-=
m_data
->
nb_sorption_sites
(
s
)
*
sorbed_species_concentration
(
s
);
}
jacobian
(
ids
,
idw
)
=
rho_w
*
tmp_w
/
factor
;
}
// component
for
(
index_t
k:
m_data
->
range_aqueous_component
())
{
const
index_t
idk
=
ideq_paq
(
k
);
if
(
idk
==
no_equation
)
continue
;
scalar_t
tmp_k
=
-
conc_w
*
diff_surface_weigthed_sum_sorbed
(
k
);
jacobian
(
ids
,
idk
)
=
tmp_k
/
factor
;
}
if
(
ideq_electron
()
!=
no_equation
)
{
scalar_t
tmp_e
=
-
conc_w
*
diff_surface_weigthed_sum_sorbed
(
m_data
->
electron_index
());
jacobian
(
ids
,
ideq_electron
())
=
tmp_e
/
factor
;
}
// water
}
void
AdimensionalSystem
::
jacobian_electron
(
Vector
&
x
,
Matrix
&
jacobian
)
{
const
auto
ide
=
ideq_electron
();
const
auto
dofe
=
m_data
->
electron_index
();
const
scalar_t
conc_w
=
density_water
()
*
saturation_water
(
x
);
const
scalar_t
factor
=
get_options
().
scaling_electron
;
// Aqueous components
for
(
index_t
k:
m_data
->
range_aqueous_component
())
{
if
(
ideq_paq
(
k
)
==
no_equation
)
continue
;
scalar_t
tmp_eip
=
0
;
tmp_eip
-=
diff_weigthed_sum_aqueous
(
k
,
dofe
);
tmp_eip
-=
diff_weigthed_sum_sorbed
(
k
,
dofe
);
tmp_eip
*=
conc_w
;
tmp_eip
-=
diff_weigthed_sum_gas
(
k
,
dofe
);
jacobian
(
ide
,
ideq_paq
(
k
))
=
tmp_eip
/
factor
;
}
// Minerals
for
(
index_t
m:
m_data
->
range_mineral
())
{
if
(
ideq_min
(
m
)
==
no_equation
)
continue
;
jacobian
(
ide
,
ideq_min
(
m
))
=
-
m_data
->
nu_mineral
(
m
,
dofe
)
/
molar_volume_mineral
(
m
)
/
factor
;
}
// Water
if
(
ideq_w
()
!=
no_equation
)
{
scalar_t
tmp_iw
=
0
;
tmp_iw
-=
weigthed_sum_aqueous
(
dofe
);
tmp_iw
-=
weigthed_sum_sorbed
(
dofe
);
tmp_iw
*=
density_water
();
jacobian
(
ide
,
ideq_w
())
=
tmp_iw
/
factor
;
}
// Surface
if
(
ideq_surf
()
!=
no_equation
)
{
scalar_t
tmp_s
=
-
conc_w
*
diff_surface_weigthed_sum_sorbed
(
dofe
);
jacobian
(
ide
,
ideq_surf
())
=
tmp_s
/
factor
;
}
// Electron
if
(
ideq_electron
()
!=
no_equation
)
{
scalar_t
tmp
=
0.0
;
tmp
-=
diff_weigthed_sum_aqueous
(
dofe
,
dofe
);
tmp
-=
diff_weigthed_sum_sorbed
(
dofe
,
dofe
);
tmp
*=
conc_w
;
tmp
-=
diff_weigthed_sum_gas
(
dofe
,
dofe
);
jacobian
(
ide
,
ide
)
=
tmp
/
factor
;
}
}
// ========================== //
// //
// Secondary variables //
// //
// ========================== //
void
AdimensionalSystem
::
set_secondary_variables
(
const
Vector
&
x
)
{
m_second
.
porosity
=
1
-
sum_saturation_minerals
(
x
)
-
m_inert_volume_fraction
;
set_saturation_gas_phase
(
x
);
set_pressure_fugacity
(
x
);
if
(
ideq_surf
()
!=
no_equation
)
set_sorbed_concentrations
(
x
);
set_secondary_concentration
(
x
);
compute_log_gamma
(
x
);
}
void
AdimensionalSystem
::
set_saturation_gas_phase
(
const
Vector
&
x
)
{
m_second
.
saturation_gas
=
m_second
.
porosity
-
saturation_water
(
x
);
//m_second.saturation_gas = 1 - saturation_water(x) - sum_saturation_minerals(x) - m_inert_volume_fraction;
}
void
AdimensionalSystem
::
set_pressure_fugacity
(
const
Vector
&
x
)
{
const
auto
rt
=
constants
::
gas_constant
*
temperature
();
for
(
index_t
k:
m_data
->
range_gas
())
{
if
(
not
is_active_gas
(
k
))
continue
;
scalar_t
logp
=
-
m_data
->
logk_gas
(
k
);
for
(
index_t
i:
m_data
->
range_aqueous_component
())
{
if
(
m_data
->
nu_gas
(
k
,
i
)
==
0.0
)
continue
;
const
auto
log_activity_i
=
log_component_molality
(
x
,
i
)
+
log_gamma_component
(
i
);
logp
+=
m_data
->
nu_gas
(
k
,
i
)
*
log_activity_i
;
}
if
(
ideq_electron
()
!=
no_equation
and
m_data
->
is_gas_half_cell_reaction
(
k
))
logp
+=
m_data
->
nu_gas
(
k
,
m_data
->
electron_index
())
*
log_activity_electron
(
x
);
m_second
.
gas_fugacity
(
k
)
=
pow10
(
logp
);
const
scalar_t
pressure
=
gas_fugacity
(
k
)
*
gas_total_pressure
();
const
scalar_t
concentration
=
m_scaling_gas
*
saturation_gas_phase
()
*
pressure
/
rt
;
m_second
.
gas_concentration
(
k
)
=
concentration
;
}
}
void
AdimensionalSystem
::
set_secondary_concentration
(
const
Vector
&
x
)
{
for
(
index_t
j:
m_data
->
range_aqueous
())
{
if
(
not
is_aqueous_active
(
j
))
{
m_second
.
secondary_molalities
(
j
)
=
0.0
;
continue
;
}
scalar_t
logconc
=
-
m_data
->
logk_aqueous
(
j
)
-
log_gamma_secondary
(
j
);
for
(
index_t
k:
m_data
->
range_aqueous_component
())
{
if
(
m_data
->
nu_aqueous
(
j
,
k
)
==
0
)
continue
;
const
auto
log_activity_k
=
log_component_molality
(
x
,
k
)
+
log_gamma_component
(
k
);
logconc
+=
m_data
->
nu_aqueous
(
j
,
k
)
*
log_activity_k
;
}
if
(
ideq_electron
()
!=
no_equation
and
m_data
->
is_half_cell_reaction
(
j
))
logconc
+=
m_data
->
nu_aqueous
(
j
,
m_data
->
electron_index
())
*
log_activity_electron
(
x
);
m_second
.
secondary_molalities
(
j
)
=
pow10
(
logconc
);
}
}
void
AdimensionalSystem
::
set_sorbed_concentrations
(
const
Vector
&
x
)
{
for
(
index_t
s:
m_data
->
range_sorbed
())
{
if
(
not
is_active_sorbed
(
s
))
{
m_second
.
sorbed_concentrations
(
s
)
=
0.0
;
continue
;
}
scalar_t
logconc
=
-
m_data
->
logk_sorbed
(
s
)
+
m_data
->
nb_sorption_sites
(
s
)
*
(
log_free_sorption_site_concentration
(
x
));
for
(
index_t
k:
m_data
->
range_aqueous_component
())
{
if
(
m_data
->
nu_sorbed
(
s
,
k
)
==
0.0
)
continue
;
const
auto
activity_k
=
log_component_molality
(
x
,
k
)
+
log_gamma_component
(
k
);
logconc
+=
m_data
->
nu_sorbed
(
s
,
k
)
*
activity_k
;
}
if
(
ideq_electron
()
!=
no_equation
and
m_data
->
is_sorbed_half_cell_reaction
(
s
))
logconc
+=
m_data
->
nu_sorbed
(
s
,
m_data
->
electron_index
())
*
log_activity_electron
(
x
);
m_second
.
sorbed_concentrations
(
s
)
=
pow10
(
logconc
);
}
}
void
AdimensionalSystem
::
set_ionic_strength
(
const
Vector
&
x
)
{
scalar_t
ionic
=
0
;
for
(
index_t
i:
m_data
->
range_aqueous_component
())
{
if
(
ideq_paq
(
i
)
==
no_equation
or
m_data
->
charge_component
(
i
)
==
0
)
continue
;
ionic
+=
component_molality
(
x
,
i
)
*
std
::
pow
(
m_data
->
charge_component
(
i
),
2
);
}
for
(
index_t
j:
m_data
->
range_aqueous
())
{
if
(
not
is_aqueous_active
(
j
)
or
m_data
->
charge_aqueous
(
j
)
==
0
)
continue
;
ionic
+=
secondary_molality
(
j
)
*
std
::
pow
(
m_data
->
charge_aqueous
(
j
),
2
);
}
ionic_strength
()
=
ionic
/
2
;
}
void
AdimensionalSystem
::
compute_log_gamma
(
const
Vector
&
x
)
{
set_ionic_strength
(
x
);
const
scalar_t
sqrti
=
std
::
sqrt
(
ionic_strength
());
for
(
index_t
i:
m_data
->
range_aqueous_component
())
{
if
(
ideq_paq
(
i
)
==
no_equation
)
{
log_gamma_component
(
i
)
=
0.0
;
continue
;
}
log_gamma_component
(
i
)
=
laws
::
extended_debye_huckel
(
ionic_strength
(),
sqrti
,
m_data
->
charge_component
(
i
),
m_data
->
a_debye_component
(
i
),
m_data
->
b_debye_component
(
i
)
);
}
for
(
index_t
j:
m_data
->
range_aqueous
())
{
if
(
not
is_aqueous_active
(
j
))
{
log_gamma_secondary
(
j
)
=
0.0
;
continue
;
}
log_gamma_secondary
(
j
)
=
laws
::
extended_debye_huckel
(
ionic_strength
(),
sqrti
,
m_data
->
charge_aqueous
(
j
),
m_data
->
a_debye_aqueous
(
j
),
m_data
->
b_debye_aqueous
(
j
)
);
}
}
bool
AdimensionalSystem
::
hook_start_iteration
(
const
Vector
&
x
,
scalar_t
norm_residual
)
{
if
(
not
get_options
().
non_ideality
)
{
set_secondary_variables
(
x
);
// we still need to compute secondary species !
// if (norm_residual < nb_free_variables()*get_options().start_non_ideality_computation)
// {
// set_secondary_variables(x);
// }
return
true
;
}
not_in_linesearch
=
true
;
scalar_t
previous_norm
=
m_second
.
loggamma
.
norm
();
if
(
previous_norm
==
0
)
previous_norm
=
1
;
bool
may_have_converged
=
false
;
if
(
norm_residual
<
nb_free_variables
()
*
get_options
().
start_non_ideality_computation
)
{
// Use fixed point iterations for non-ideality
for
(
int
i
=
0
;
i
<
get_options
().
non_ideality_max_iter
;
++
i
)
{
set_secondary_variables
(
x
);
compute_log_gamma
(
x
);
// convergence check
if
(
std
::
abs
(
previous_norm
-
m_second
.
loggamma
.
norm
())
/
previous_norm
<
get_options
().
non_ideality_tolerance
)
{
may_have_converged
=
true
;
break
;
}
previous_norm
=
m_second
.
loggamma
.
norm
();
}
}
return
may_have_converged
;
}
double
AdimensionalSystem
::
max_lambda
(
const
Vector
&
x
,
const
Vector
&
update
)
{
if
(
ideq_w
()
!=
no_equation
)
{
return
1.0
/
std
::
max
(
1.0
,
-
update
(
0
)
/
(
get_options
().
under_relaxation_factor
*
x
(
0
)));
}
else
{
return
1.0
;
}
}
AdimensionalSystemSolution
AdimensionalSystem
::
get_solution
(
Vector
&
xtot
,
const
Vector
&
x
)
{
double
previous_norm
=
m_second
.
loggamma
.
norm
();
set_saturation_gas_phase
(
x
);
set_pressure_fugacity
(
x
);
set_secondary_concentration
(
x
);
if
(
ideq_surf
()
!=
no_equation
)
set_sorbed_concentrations
(
x
);
if
(
get_options
().
non_ideality
)
{
compute_log_gamma
(
x
);
if
(
std
::
abs
(
previous_norm
-
m_second
.
loggamma
.
norm
())
>
1e-6
)
{
WARNING
<<
"Activity coefficient have not converged !"
<<
std
::
endl
<<
"output can not be trusted
\n
Difference : "
+
std
::
to_string
(
std
::
abs
(
previous_norm
-
m_second
.
loggamma
.
norm
()));
}
}
// Set the correct value for the water total saturation
if
(
ideq_w
()
==
no_equation
)
{
xtot
(
dof_water
())
=
saturation_water
(
x
);
}
return
AdimensionalSystemSolution
(
xtot
,
m_second
.
secondary_molalities
,
m_second
.
loggamma
,
m_second
.
ionic_strength
,
m_second
.
gas_fugacity
,
m_second
.
sorbed_concentrations
,
m_inert_volume_fraction
);
}
// Water, saturation and density
// ==============================
scalar_t
AdimensionalSystem
::
density_water
()
const
{
return
laws
::
density_water
(
units
::
celsius
(
25.0
),
length_unit
(),
mass_unit
());
}
scalar_t
AdimensionalSystem
::
saturation_water
(
const
Vector
&
x
)
const
{
if
(
ideq_w
()
!=
no_equation
)
return
x
(
ideq_w
());
else
return
1.0
-
sum_saturation_minerals
(
x
)
-
m_inert_volume_fraction
;
}
scalar_t
AdimensionalSystem
::
saturation_mineral
(
const
Vector
&
x
,
index_t
mineral
)
const
{
specmicp_assert
(
mineral
>=
0
and
mineral
<
m_data
->
nb_mineral
());
if
(
ideq_min
(
mineral
)
==
no_equation
)
return
0.0
;
else
return
x
(
ideq_min
(
mineral
));
}
scalar_t
AdimensionalSystem
::
sum_saturation_minerals
(
const
Vector
&
x
)
const
{
scalar_t
sum_saturations
=
0.0
;
for
(
index_t
mineral:
m_data
->
range_mineral
())
{
sum_saturations
+=
saturation_mineral
(
x
,
mineral
);
}
return
sum_saturations
;
}
// Starting guess
// ==============
void
AdimensionalSystem
::
reasonable_starting_guess
(
Vector
&
xtot
)
{
xtot
.
resize
(
total_dofs
());
xtot
(
dof_water
())
=
0.8
;
for
(
index_t
i:
m_data
->
range_aqueous_component
())
{
xtot
(
dof_component
(
i
))
=
-
4.0
;
}
if
(
ideq_surf
()
!=
no_equation
)
xtot
(
dof_surface
())
=
std
::
log10
(
0.8
*
surface_total_concentration
());
else
xtot
(
dof_surface
())
=
-
HUGE_VAL
;
if
(
ideq_electron
()
!=
no_equation
)
xtot
(
dof_electron
())
=
-
4
;
else
xtot
(
dof_electron
())
=
-
HUGE_VAL
;
xtot
.
segment
(
offset_minerals
(),
m_data
->
nb_mineral
()).
setZero
();
m_second
=
SecondaryVariables
(
m_data
);
}
void
AdimensionalSystem
::
reasonable_restarting_guess
(
Vector
&
xtot
)
{
std
::
random_device
rd
;
std
::
mt19937
gen
(
rd
());
std
::
uniform_real_distribution
<>
dis
(
-
2
,
2
);
xtot
(
dof_water
())
=
0.5
;
for
(
index_t
i:
m_data
->
range_aqueous_component
())
{
//if (xtot(dof_component(i)) > 0 or xtot(dof_component(i)) < -9)
xtot
(
i
)
=
get_options
().
restart_concentration
+
dis
(
gen
);
}
if
(
ideq_surf
()
!=
no_equation
)
xtot
(
dof_surface
())
=
std
::
log10
(
0.8
*
surface_total_concentration
());
else
xtot
(
dof_surface
())
=
-
HUGE_VAL
;
if
(
ideq_electron
()
!=
no_equation
)
xtot
(
dof_electron
())
=
-
4
;
else
xtot
(
dof_electron
())
=
-
HUGE_VAL
;
xtot
.
segment
(
offset_minerals
(),
m_data
->
nb_mineral
()).
setZero
();
m_second
=
SecondaryVariables
(
m_data
);
}
}
// end namespace specmicp
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