PorousFlowBrineCO2 Class Reference

Specialized class for brine and CO2 including calculation of mutual solubility of the two fluids using a high-accuracy fugacity-based formulation. More...

#include <PorousFlowBrineCO2.h>

Inheritance diagram for PorousFlowBrineCO2:

Public Member Functions
	PorousFlowBrineCO2 (const InputParameters &parameters)
virtual std::string	fluidStateName () const override
	Name of FluidState. More...
virtual void	thermophysicalProperties (Real pressure, Real temperature, Real Xnacl, Real Z, unsigned int qp, std::vector< FluidStateProperties > &fsp) const override
	Determines the complete thermophysical state of the system for a given set of primary variables. More...
void	equilibriumMoleFractions (Real pressure, Real temperature, Real Xnacl, Real &xco2, Real &dxco2_dp, Real &dxco2_dT, Real &dxco2_dX, Real &yh2o, Real &dyh2o_dp, Real &dyh2o_dT, Real &dyh2o_dX) const
	Mole fractions of CO2 in brine and water vapor in CO2 at equilibrium. More...
void	equilibriumMassFractions (Real pressure, Real temperature, Real Xnacl, Real &Xco2, Real &dXco2_dp, Real &dXco2_dT, Real &dXco2_dX, Real &Yh2o, Real &dYh2o_dp, Real &dYh2o_dT, Real &dYh2o_dX) const
	Mass fractions of CO2 in brine and water vapor in CO2 at equilibrium. More...
void	massFractions (Real pressure, Real temperature, Real Xnacl, Real Z, FluidStatePhaseEnum &phase_state, std::vector< FluidStateProperties > &fsp) const
	Mass fractions of CO2 and H2O in both phases, as well as derivatives wrt PorousFlow variables. More...
void	gasProperties (Real pressure, Real temperature, std::vector< FluidStateProperties > &fsp) const
	Thermophysical properties of the gaseous state. More...
void	liquidProperties (Real pressure, Real temperature, Real Xnacl, std::vector< FluidStateProperties > &fsp) const
	Thermophysical properties of the liquid state. More...
void	saturationTwoPhase (Real pressure, Real temperature, Real Xnacl, Real Z, std::vector< FluidStateProperties > &fsp) const
	Gas and liquid saturations for the two-phase region. More...
void	fugacityCoefficientsLowTemp (Real pressure, Real temperature, Real co2_density, Real dco2_density_dp, Real dco2_density_dT, Real &fco2, Real &dfco2_dp, Real &dfco2_dT, Real &fh2o, Real &dfh2o_dp, Real &dfh2o_dT) const
	Fugacity coefficients for H2O and CO2 for T <= 100C Eq. More...
Real	activityCoefficientH2O (Real temperature, Real xco2) const
	Activity coefficient of H2O Eq. More...
Real	activityCoefficientCO2 (Real temperature, Real xco2) const
	Activity coefficient of CO2 Eq. More...
void	activityCoefficient (Real pressure, Real temperature, Real Xnacl, Real &gamma, Real &dgamma_dp, Real &dgamma_dT, Real &dgamma_dX) const
	Activity coefficient for CO2 in brine. More...
void	activityCoefficientHighTemp (Real temperature, Real Xnacl, Real &gamma, Real &dgamma_dT, Real &dgamma_dX) const
	Activity coefficient for CO2 in brine used in the elevated temperature formulation. More...
void	equilibriumConstantH2O (Real temperature, Real &kh2o, Real &dkh2o_dT) const
	Equilibrium constant for H2O For temperatures 12C <= T <= 99C, uses Spycher, Pruess and Ennis-King (2003) For temperatures 109C <= T <= 300C, uses Spycher and Pruess (2010) For temperatures 99C < T < 109C, the value is calculated by smoothly interpolating the two formulations. More...
void	equilibriumConstantCO2 (Real temperature, Real &kco2, Real &dkco2_dT) const
	Equilibrium constant for CO2 For temperatures 12C <= T <= 99C, uses Spycher, Pruess and Ennis-King (2003) For temperatures 109C <= T <= 300C, uses Spycher and Pruess (2010) For temperatures 99C < T < 109C, the value is calculated by smoothly interpolating the two formulations. More...
void	partialDensityCO2 (Real temperature, Real &partial_density, Real &dpartial_density_dT) const
	Partial density of dissolved CO2 From Garcia, Density of aqueous solutions of CO2, LBNL-49023 (2001) More...
virtual Real	totalMassFraction (Real pressure, Real temperature, Real Xnacl, Real saturation, unsigned int qp) const override
	Total mass fraction of fluid component summed over all phases in the two-phase state for a specified gas saturation. More...
unsigned int	saltComponentIndex () const
	The index of the salt component. More...
void	henryConstant (Real temperature, Real Xnacl, Real &Kh, Real &dKh_dT, Real &dKh_dx) const
	Henry's constant of dissolution of gas phase CO2 in brine. More...
void	enthalpyOfDissolutionGas (Real temperature, Real Xnacl, Real &hdis, Real &dhdis_dT, Real &dhdis_dx) const
	Enthalpy of dissolution of gas phase CO2 in brine calculated using Henry's constant From Himmelblau, Partial molal heats and entropies of solution for gases dissolved in water from the freezing to the near critical point, J. More...
void	enthalpyOfDissolution (Real temperature, Real &hdis, Real &dhdis_dT) const
	Enthalpy of dissolution of CO2 in brine calculated using linear fit to model of Duan and Sun, An improved model calculating CO2 solubility in pure water and aqueous NaCl solutions from 273 to 533 K and from 0 to 2000 bar, Chemical geology, 193, 257–271 (2003). More...
void	equilibriumMoleFractionsLowTemp (Real pressure, Real temperature, Real Xnacl, Real &xco2, Real &dxco2_dp, Real &dxco2_dT, Real &dxco2_dX, Real &yh2o, Real &dyh2o_dp, Real &dyh2o_dT, Real &dyh2o_dX) const
	Mole fractions of CO2 in brine and water vapor in CO2 at equilibrium in the low temperature regime (T <= 99C). More...
void	solveEquilibriumMoleFractionHighTemp (Real pressure, Real temperature, Real Xnacl, Real co2_density, Real &xco2, Real &yh2o) const
	Function to solve for yh2o and xco2 iteratively in the elevated temperature regime (T > 100C) More...
unsigned int	numPhases () const
	The maximum number of phases in this model. More...
unsigned int	numComponents () const
	The maximum number of components in this model. More...
unsigned int	aqueousPhaseIndex () const
	The index of the aqueous phase. More...
unsigned int	gasPhaseIndex () const
	The index of the gas phase. More...
unsigned int	aqueousComponentIndex () const
	The index of the aqueous fluid component. More...
unsigned int	gasComponentIndex () const
	The index of the gas fluid component. More...
void	clearFluidStateProperties (std::vector< FluidStateProperties > &fsp) const
	Clears the contents of the FluidStateProperties data structure. More...
void	initialize () final
void	execute () final
void	finalize () final
Real	rachfordRice (Real vf, std::vector< Real > &Zi, std::vector< Real > &Ki) const
	Rachford-Rice equation for vapor fraction. More...
Real	rachfordRiceDeriv (Real vf, std::vector< Real > &Zi, std::vector< Real > &Ki) const
	Derivative of Rachford-Rice equation wrt vapor fraction. More...
Real	vaporMassFraction (Real Z0, Real K0, Real K1) const
	Solves Rachford-Rice equation to provide vapor mass fraction. More...
Real	vaporMassFraction (std::vector< Real > &Zi, std::vector< Real > &Ki) const
void	fugacityCoefficientsHighTemp (Real pressure, Real temperature, Real co2_density, Real xco2, Real yh2o, Real &fco2, Real &fh2o) const
	Fugacity coefficients for H2O and CO2 at elevated temperatures (100C < T <= 300C). More...
void	fugacityCoefficientsHighTemp (Real pressure, Real temperature, Real co2_density, Real xco2, Real yh2o, Real &fco2, Real &dfco2_dp, Real &dfco2_dT, Real &fh2o, Real &dfh2o_dp, Real &dfh2o_dT) const
Real	fugacityCoefficientH2OHighTemp (Real pressure, Real temperature, Real co2_density, Real xco2, Real yh2o) const
Real	fugacityCoefficientCO2HighTemp (Real pressure, Real temperature, Real co2_density, Real xco2, Real yh2o) const

Protected Member Functions
void	checkVariables (Real pressure, Real temperature) const
	Check the input variables. More...
void	smoothCubicInterpolation (Real temperature, Real f0, Real df0, Real f1, Real df1, Real &value, Real &deriv) const
	Cubic function to smoothly interpolate between the low temperature and elevated temperature models for 99C < T < 109C. More...
void	phaseState (Real Zi, Real Xi, Real Yi, FluidStatePhaseEnum &phase_state) const
	Determines the phase state gven the total mass fraction and equilibrium mass fractions. More...
void	funcABHighTemp (Real pressure, Real temperature, Real Xnacl, Real co2_density, Real xco2, Real yh2o, Real &A, Real &B) const
	The function A (Eq. More...
void	funcABHighTemp (Real pressure, Real temperature, Real Xnacl, Real co2_density, Real xco2, Real yh2o, Real &A, Real &dA_dp, Real &dA_dT, Real &B, Real &dB_dp, Real &dB_dT, Real &dB_dX) const
void	funcABLowTemp (Real pressure, Real temperature, Real co2_density, Real dco2_density_dp, Real dco2_density_dT, Real &A, Real &dA_dp, Real &dA_dT, Real &B, Real &dB_dp, Real &dB_dT) const

Protected Attributes
const unsigned int	_salt_component
	Salt component index. More...
const BrineFluidProperties &	_brine_fp
	Fluid properties UserObject for water. More...
const SinglePhaseFluidProperties &	_co2_fp
	Fluid properties UserObject for the CO2. More...
const SinglePhaseFluidProperties &	_water_fp
	Fluid properties UserObject for H20. More...
const Real	_Mh2o
	Molar mass of water (kg/mol) More...
const Real	_invMh2o
	Inverse of molar mass of H2O (mol/kg) More...
const Real	_Mco2
	Molar mass of CO2 (kg/mol) More...
const Real	_Mnacl
	Molar mass of NaCL. More...
const Real	_Rbar
	Molar gas constant in bar cm^3 /(K mol) More...
const Real	_Tlower
	Temperature below which the Spycher, Pruess & Ennis-King (2003) model is used (K) More...
const Real	_Tupper
	Temperature above which the Spycher & Pruess (2010) model is used (K) More...
unsigned int	_num_phases
	Number of phases. More...
unsigned int	_num_components
	Number of components. More...
const unsigned int	_aqueous_phase_number
	Phase number of the aqueous phase. More...
unsigned int	_gas_phase_number
	Phase number of the gas phase. More...
const unsigned int	_aqueous_fluid_component
	Fluid component number of the aqueous component. More...
unsigned int	_gas_fluid_component
	Fluid component number of the gas phase. More...
const Real	_R
	Universal gas constant (J/mol/K) More...
const Real	_T_c2k
	Conversion from C to K. More...
const Real	_nr_max_its
	Maximum number of iterations for the Newton-Raphson iterations. More...
const Real	_nr_tol
	Tolerance for Newton-Raphson iterations. More...
const PorousFlowCapillaryPressure &	_pc
	Capillary pressure UserObject. More...

Detailed Description

Specialized class for brine and CO2 including calculation of mutual solubility of the two fluids using a high-accuracy fugacity-based formulation.

For temperatures 12C <= T <= 99C, the formulation is based on Spycher, Pruess and Ennis-King, CO2-H2O mixtures in the geological sequestration of CO2. I. Assessment and calculation of mutual solubilities from 12 to 100C and up to 600 bar, Geochimica et Cosmochimica Acta, 67, 3015-3031 (2003), and Spycher and Pruess, CO2-H2O mixtures in the geological sequestration of CO2. II. Partitioning in chloride brine at 12-100C and up to 600 bar, Geochimica et Cosmochimica Acta, 69, 3309-3320 (2005).

For temperatures 109C <= T <= 300C, the formulation is based on Spycher and Pruess, A Phase-Partitioning Model for CO2-Brine Mixtures at Elevated Temperatures and Pressures: Application to CO2-Enhanced Geothermal Systems, Transport in Porous Media, 82, 173-196 (2010)

As the two formulations do not coincide at temperatures near 100C, a cubic polynomial is used in the intermediate temperature range 99C < T < 109C to provide a smooth transition from the two formulations in this region.

Notation convention Throughout this class, both mole fractions and mass fractions will be used. The following notation will be used: yk: mole fraction of component k in the gas phase xk: mole fraction of component k in the liquid phase Yk: mass fraction of component k in the gas phase Xk: mass fraction of component k in the liquid phase

Definition at line 51 of file PorousFlowBrineCO2.h.

Constructor & Destructor Documentation

PorousFlowBrineCO2()

PorousFlowBrineCO2::PorousFlowBrineCO2

(

const InputParameters &

parameters

)

Definition at line 30 of file PorousFlowBrineCO2.C.

  : PorousFlowFluidStateBase(parameters),
    _salt_component(getParam<unsigned int>("salt_component")),
    _brine_fp(getUserObject<BrineFluidProperties>("brine_fp")),
    _co2_fp(getUserObject<SinglePhaseFluidProperties>("co2_fp")),
    _water_fp(_brine_fp.getComponent(BrineFluidProperties::WATER)),
    _Mh2o(_brine_fp.molarMassH2O()),
    _invMh2o(1.0 / _Mh2o),
    _Mco2(_co2_fp.molarMass()),
    _Mnacl(_brine_fp.molarMassNaCl()),
    _Rbar(_R * 10.0),
    _Tlower(372.15),
    _Tupper(382.15)
{
  // Check that the correct FluidProperties UserObjects have been provided
  if (_co2_fp.fluidName() != "co2")
    paramError("co2_fp", "A valid CO2 FluidProperties UserObject must be provided");

  if (_brine_fp.fluidName() != "brine")
    paramError("brine_fp", "A valid Brine FluidProperties UserObject must be provided");

  // Set the number of phases and components, and their indexes
  _num_phases = 2;
  _num_components = 3;
  _gas_phase_number = 1 - _aqueous_phase_number;
  _gas_fluid_component = 3 - _aqueous_fluid_component - _salt_component;

  // Check that _aqueous_phase_number is <= total number of phases
  if (_aqueous_phase_number >= _num_phases)
    paramError("liquid_phase_number",
               "This value is larger than the possible number of phases ",
               _num_phases);

  // Check that _aqueous_fluid_component is <= total number of fluid components
  if (_aqueous_fluid_component >= _num_components)
    paramError("liquid_fluid_component",
               "This value is larger than the possible number of fluid components",
               _num_components);

  // Check that the salt component index is not identical to the liquid fluid component
  if (_salt_component == _aqueous_fluid_component)
    paramError(
        "salt_component",
        "The value provided must be different from the value entered in liquid_fluid_component");

  // Check that _salt_component is <= total number of fluid components
  if (_salt_component >= _num_components)
    paramError("salt_component",
               "The value provided is larger than the possible number of fluid components",
               _num_components);
}

Member Function Documentation

activityCoefficient()

void PorousFlowBrineCO2::activityCoefficient	(	Real	pressure,
		Real	temperature,
		Real	Xnacl,
		Real &	gamma,
		Real &	dgamma_dp,
		Real &	dgamma_dT,
		Real &	dgamma_dX
	)		const

Activity coefficient for CO2 in brine.

From Duan and Sun, An improved model calculating CO2 solubility in pure water and aqueous NaCl solutions from 257 to 533 K and from 0 to 2000 bar, Chem. Geol., 193, 257-271 (2003)

Note: this is not a 'true' activity coefficient, and is instead related to the molality of CO2 in water and brine. Nevertheless, Spycher and Pruess (2005) refer to it as an activity coefficient, so this notation is followed here.

Parameters

	pressure	phase pressure (Pa)
	temperature	phase temperature (K)
	Xnacl	salt mass fraction (kg/kg)
[out]	gamma	activity coefficient for CO2 in brine
[out]	dgamma_dp	derivative of activity coefficient wrt pressure
[out]	dgamma_dT	derivative of activity coefficient wrt temperature
[out]	dgamma_dX	derivative of activity coefficient wrt salt mass fraction

Definition at line 835 of file PorousFlowBrineCO2.C.

Referenced by equilibriumMoleFractionsLowTemp().

{
  // Need pressure in bar
  const Real pbar = pressure * 1.0e-5;
  // Need NaCl molality (mol/kg)
  const Real mnacl = Xnacl / (1.0 - Xnacl) / _Mnacl;
  const Real dmnacl_dX = 1.0 / (1.0 - Xnacl) / (1.0 - Xnacl) / _Mnacl;

  const Real lambda = -0.411370585 + 6.07632013e-4 * temperature + 97.5347708 / temperature -
                      0.0237622469 * pbar / temperature +
                      0.0170656236 * pbar / (630.0 - temperature) +
                      1.41335834e-5 * temperature * std::log(pbar);

  const Real xi = 3.36389723e-4 - 1.9829898e-5 * temperature + 2.12220830e-3 * pbar / temperature -
                  5.24873303e-3 * pbar / (630.0 - temperature);

  gamma = std::exp(2.0 * lambda * mnacl + xi * mnacl * mnacl);

  // Derivative wrt pressure
  const Real dlambda_dp = -0.0237622469 / temperature + 0.0170656236 / (630.0 - temperature) +
                          1.41335834e-5 * temperature / pbar;
  const Real dxi_dp = 2.12220830e-3 / temperature - 5.24873303e-3 / (630.0 - temperature);
  dgamma_dp = (2.0 * mnacl * dlambda_dp + mnacl * mnacl * dxi_dp) * gamma * 1.0e-5;

  // Derivative wrt temperature
  const Real dlambda_dT = 6.07632013e-4 - 97.5347708 / temperature / temperature +
                          0.0237622469 * pbar / temperature / temperature +
                          0.0170656236 * pbar / (630.0 - temperature) / (630.0 - temperature) +
                          1.41335834e-5 * std::log(pbar);
  const Real dxi_dT = -1.9829898e-5 - 2.12220830e-3 * pbar / temperature / temperature -
                      5.24873303e-3 * pbar / (630.0 - temperature) / (630.0 - temperature);
  dgamma_dT = (2.0 * mnacl * dlambda_dT + mnacl * mnacl * dxi_dT) * gamma;

  // Derivative wrt salt mass fraction
  dgamma_dX = (2.0 * lambda * dmnacl_dX + 2.0 * xi * mnacl * dmnacl_dX) * gamma;
}

activityCoefficientCO2()

Real PorousFlowBrineCO2::activityCoefficientCO2	(	Real	temperature,
		Real	xco2
	)		const

Activity coefficient of CO2 Eq.

(13) from Spycher & Pruess (2010)

Parameters

temperature	temperature (K)
xco2	mole fraction of CO2 in liquid phase (-)

Returns

activity coefficient

Definition at line 820 of file PorousFlowBrineCO2.C.

Referenced by funcABHighTemp().

{
  if (temperature <= 373.15)
    return 1.0;
  else
  {
    const Real Tref = temperature - 373.15;
    const Real xh2o = 1.0 - xco2;
    const Real Am = -3.084e-2 * Tref + 1.927e-5 * Tref * Tref;

    return std::exp(2.0 * Am * xco2 * xh2o * xh2o);
  }
}

activityCoefficientH2O()

Real PorousFlowBrineCO2::activityCoefficientH2O	(	Real	temperature,
		Real	xco2
	)		const

Activity coefficient of H2O Eq.

(12) from Spycher & Pruess (2010)

Parameters

temperature	temperature (K)
xco2	mole fraction of CO2 in liquid phase (-)

Returns

activity coefficient

Definition at line 805 of file PorousFlowBrineCO2.C.

Referenced by funcABHighTemp().

{
  if (temperature <= 373.15)
    return 1.0;
  else
  {
    const Real Tref = temperature - 373.15;
    const Real xh2o = 1.0 - xco2;
    const Real Am = -3.084e-2 * Tref + 1.927e-5 * Tref * Tref;

    return std::exp((Am - 2.0 * Am * xh2o) * xco2 * xco2);
  }
}

activityCoefficientHighTemp()

void PorousFlowBrineCO2::activityCoefficientHighTemp	(	Real	temperature,
		Real	Xnacl,
		Real &	gamma,
		Real &	dgamma_dT,
		Real &	dgamma_dX
	)		const

Activity coefficient for CO2 in brine used in the elevated temperature formulation.

Eq. (18) from Spycher and Pruess (2010).

Note: unlike activityCoefficient(), no pressure dependence is included in this formulation

Parameters

	temperature	phase temperature (K)
	Xnacl	salt mass fraction (kg/kg)
[out]	gamma	activity coefficient for CO2 in brine
[out]	dgamma_dT	derivative of activity coefficient wrt temperature
[out]	dgamma_dX	derivative of activity coefficient wrt salt mass fraction

Definition at line 879 of file PorousFlowBrineCO2.C.

Referenced by funcABHighTemp().

{
  // Need NaCl molality (mol/kg)
  const Real mnacl = Xnacl / (1.0 - Xnacl) / _Mnacl;
  const Real dmnacl_dX = 1.0 / (1.0 - Xnacl) / (1.0 - Xnacl) / _Mnacl;

  const Real T2 = temperature * temperature;
  const Real T3 = temperature * T2;

  const Real lambda = 2.217e-4 * temperature + 1.074 / temperature + 2648.0 / T2;
  const Real xi = 1.3e-5 * temperature - 20.12 / temperature + 5259.0 / T2;

  gamma = (1.0 - mnacl / _invMh2o) * std::exp(2.0 * lambda * mnacl + xi * mnacl * mnacl);

  // Derivative wrt temperature
  const Real dlambda_dT = 2.217e-4 - 1.074 / T2 - 5296.0 / T3;
  const Real dxi_dT = 1.3e-5 + 20.12 / T2 - 10518.0 / T3;
  dgamma_dT = (2.0 * mnacl * dlambda_dT + mnacl * mnacl * dxi_dT) * gamma;

  // Derivative wrt salt mass fraction
  dgamma_dX = (2.0 * lambda * dmnacl_dX + 2.0 * xi * mnacl * dmnacl_dX) * gamma -
              dmnacl_dX / _invMh2o * std::exp(2.0 * lambda * mnacl + xi * mnacl * mnacl);
}

aqueousComponentIndex()

unsigned int PorousFlowFluidStateBase::aqueousComponentIndex ( ) const

inlineinherited

The index of the aqueous fluid component.

Returns

aqueous fluid component number

Definition at line 117 of file PorousFlowFluidStateBase.h.

{ return _aqueous_fluid_component; };

aqueousPhaseIndex()

unsigned int PorousFlowFluidStateBase::aqueousPhaseIndex ( ) const

inlineinherited

The index of the aqueous phase.

Returns

aqueous phase number

Definition at line 105 of file PorousFlowFluidStateBase.h.

{ return _aqueous_phase_number; };

checkVariables()

void PorousFlowBrineCO2::checkVariables ( Real  pressure, Real  temperature  ) const

protected

Check the input variables.

Definition at line 1541 of file PorousFlowBrineCO2.C.

Referenced by thermophysicalProperties(), and totalMassFraction().

{
  // The calculation of mass fractions is valid from 12C <= T <= 300C, and
  // pressure less than 60 MPa
  if (temperature < 285.15 || temperature > 573.15)
    mooseException(name() + ": temperature " + Moose::stringify(temperature) +
                   " is outside range 285.15 K <= T <= 573.15 K");

  if (pressure > 6.0e7)
    mooseException(name() + ": pressure " + Moose::stringify(pressure) +
                   " must be less than 60 MPa");
}

clearFluidStateProperties()

void PorousFlowFluidStateBase::clearFluidStateProperties ( std::vector< FluidStateProperties > &  fsp ) const

inherited

Clears the contents of the FluidStateProperties data structure.

Parameters

[out]

fsp

FluidStateProperties data structure with all data initialized to 0

Definition at line 41 of file PorousFlowFluidStateBase.C.

Referenced by PorousFlowWaterNCG::thermophysicalProperties(), and thermophysicalProperties().

{
  std::fill(fsp.begin(), fsp.end(), FluidStateProperties(_num_components));
}

enthalpyOfDissolution()

void PorousFlowBrineCO2::enthalpyOfDissolution	(	Real	temperature,
		Real &	hdis,
		Real &	dhdis_dT
	)		const

Enthalpy of dissolution of CO2 in brine calculated using linear fit to model of Duan and Sun, An improved model calculating CO2 solubility in pure water and aqueous NaCl solutions from 273 to 533 K and from 0 to 2000 bar, Chemical geology, 193, 257–271 (2003).

In the region of interest, the more complicated model given in Eq. (8) of Duan and Sun is well approximated by a simple linear fit (R^2 = 0.9997).

Note: as the effect of salt mass fraction is small, it is not included in this function.

Parameters

	temperature	fluid temperature (K)
[out]	hdis	enthalpy of dissolution (J/kg)
[out]	dhdis_dT	derivative of enthalpy of dissolution wrt temperature

Definition at line 1511 of file PorousFlowBrineCO2.C.

Referenced by liquidProperties().

{
  // Linear fit to model of Duan and Sun (2003) (in kJ/mol)
  const Real delta_h = -58.3533 + 0.134519 * temperature;

  // Convert to J/kg
  hdis = delta_h * 1000.0 / _Mco2;
  dhdis_dT = 134.519 / _Mco2;
}

enthalpyOfDissolutionGas()

void PorousFlowBrineCO2::enthalpyOfDissolutionGas	(	Real	temperature,
		Real	Xnacl,
		Real &	hdis,
		Real &	dhdis_dT,
		Real &	dhdis_dx
	)		const

Enthalpy of dissolution of gas phase CO2 in brine calculated using Henry's constant From Himmelblau, Partial molal heats and entropies of solution for gases dissolved in water from the freezing to the near critical point, J.

Phys. Chem. 63 (1959). Correction due to salinity from Battistelli et al, A fluid property module for the TOUGH2 simulator for saline brines with non-condensible gas, Proc. Eighteenth Workshop on Geothermal Reservoir Engineering (1993).

Parameters

	temperature	fluid temperature (K)
	Xnacl	NaCl mass fraction (kg/kg)
[out]	hdis	enthalpy of dissolution (J/kg)
[out]	dhdis_dT	derivative of enthalpy of dissolution wrt temperature
[out]	dhdis_dx	derivative of enthalpy of dissolution wrt salt mass fraction

Definition at line 1486 of file PorousFlowBrineCO2.C.

{
  // Henry's constant
  Real Kh, dKh_dT, dKh_dX;
  henryConstant(temperature, Xnacl, Kh, dKh_dT, dKh_dX);

  hdis = -_R * temperature * temperature * dKh_dT / Kh / _Mco2;

  // Derivative of enthalpy of dissolution wrt temperature and xnacl requires the second
  // derivatives of Henry's constant. For simplicity, approximate these numerically
  const Real dT = temperature * 1.0e-8;
  const Real T2 = temperature + dT;
  henryConstant(T2, Xnacl, Kh, dKh_dT, dKh_dX);

  dhdis_dT = (-_R * T2 * T2 * dKh_dT / Kh / _Mco2 - hdis) / dT;

  const Real dX = Xnacl * 1.0e-8;
  const Real X2 = Xnacl + dX;
  henryConstant(temperature, X2, Kh, dKh_dT, dKh_dX);

  dhdis_dX = (-_R * temperature * temperature * dKh_dT / Kh / _Mco2 - hdis) / dX;
}

equilibriumConstantCO2()

void PorousFlowBrineCO2::equilibriumConstantCO2	(	Real	temperature,
		Real &	kco2,
		Real &	dkco2_dT
	)		const

Equilibrium constant for CO2 For temperatures 12C <= T <= 99C, uses Spycher, Pruess and Ennis-King (2003) For temperatures 109C <= T <= 300C, uses Spycher and Pruess (2010) For temperatures 99C < T < 109C, the value is calculated by smoothly interpolating the two formulations.

Parameters

	temperature	temperature (K)
[out]	kco2	equilibrium constant for CO2
[out]	dkco2_dT	derivative of equilibrium constant wrt temperature

Definition at line 938 of file PorousFlowBrineCO2.C.

Referenced by funcABHighTemp(), and funcABLowTemp().

{
  // Uses temperature in Celcius
  const Real Tc = temperature - _T_c2k;
  const Real Tc2 = Tc * Tc;
  const Real Tc3 = Tc2 * Tc;

  Real logK0CO2, dlogK0CO2;

  if (Tc <= 99.0)
  {
    logK0CO2 = 1.189 + 1.304e-2 * Tc - 5.446e-5 * Tc2;
    dlogK0CO2 = 1.304e-2 - 1.0892e-4 * Tc;
  }
  else if (Tc > 99.0 && Tc < 109.0)
  {
    const Real Tint = (Tc - 99.0) / 10.0;
    const Real Tint2 = Tint * Tint;
    logK0CO2 = 1.9462 + 2.25692e-2 * Tint - 9.49577e-3 * Tint2 - 6.77721e-3 * Tint * Tint2;
    dlogK0CO2 = 2.25692e-2 - 1.899154e-2 * Tint + 2.033163e-2 * Tint2;
  }
  else // 109 <= Tc <= 300
  {
    logK0CO2 = 1.668 + 3.992e-3 * Tc - 1.156e-5 * Tc2 + 1.593e-9 * Tc3;
    dlogK0CO2 = 3.992e-3 - 2.312e-5 * Tc + 4.779e-9 * Tc2;
  }

  kco2 = std::pow(10.0, logK0CO2);
  dkco2_dT = std::log(10.0) * dlogK0CO2 * kco2;
}

equilibriumConstantH2O()

void PorousFlowBrineCO2::equilibriumConstantH2O	(	Real	temperature,
		Real &	kh2o,
		Real &	dkh2o_dT
	)		const

Equilibrium constant for H2O For temperatures 12C <= T <= 99C, uses Spycher, Pruess and Ennis-King (2003) For temperatures 109C <= T <= 300C, uses Spycher and Pruess (2010) For temperatures 99C < T < 109C, the value is calculated by smoothly interpolating the two formulations.

Parameters

	temperature	temperature (K)
[out]	kh2o	equilibrium constant for H2O
[out]	dkh2o_dT	derivative of equilibrium constant wrt temperature

Definition at line 905 of file PorousFlowBrineCO2.C.

Referenced by funcABHighTemp(), and funcABLowTemp().

{
  // Uses temperature in Celcius
  const Real Tc = temperature - _T_c2k;
  const Real Tc2 = Tc * Tc;
  const Real Tc3 = Tc2 * Tc;
  const Real Tc4 = Tc3 * Tc;

  Real logK0H2O, dlogK0H2O;

  if (Tc <= 99.0)
  {
    logK0H2O = -2.209 + 3.097e-2 * Tc - 1.098e-4 * Tc2 + 2.048e-7 * Tc3;
    dlogK0H2O = 3.097e-2 - 2.196e-4 * Tc + 6.144e-7 * Tc2;
  }
  else if (Tc > 99.0 && Tc < 109.0)
  {
    const Real Tint = (Tc - 99.0) / 10.0;
    const Real Tint2 = Tint * Tint;
    logK0H2O = -0.0204026 + 0.0152513 * Tint + 0.417565 * Tint2 - 0.278636 * Tint * Tint2;
    dlogK0H2O = 0.0152513 + 0.83513 * Tint - 0.835908 * Tint2;
  }
  else // 109 <= Tc <= 300
  {
    logK0H2O = -2.1077 + 2.8127e-2 * Tc - 8.4298e-5 * Tc2 + 1.4969e-7 * Tc3 - 1.1812e-10 * Tc4;
    dlogK0H2O = 2.8127e-2 - 1.68596e-4 * Tc + 4.4907e-7 * Tc2 - 4.7248e-10 * Tc3;
  }

  kh2o = std::pow(10.0, logK0H2O);
  dkh2o_dT = std::log(10.0) * dlogK0H2O * kh2o;
}

equilibriumMassFractions()

void PorousFlowBrineCO2::equilibriumMassFractions	(	Real	pressure,
		Real	temperature,
		Real	Xnacl,
		Real &	Xco2,
		Real &	dXco2_dp,
		Real &	dXco2_dT,
		Real &	dXco2_dX,
		Real &	Yh2o,
		Real &	dYh2o_dp,
		Real &	dYh2o_dT,
		Real &	dYh2o_dX
	)		const

Mass fractions of CO2 in brine and water vapor in CO2 at equilibrium.

Parameters

	pressure	phase pressure (Pa)
	temperature	phase temperature (K)
	Xnacl	NaCl mass fraction (kg/kg)
[out]	Xco2	mass fraction of CO2 in liquid (kg/kg)
[out]	dXco2_dp	derivative of mass fraction of CO2 in liquid wrt pressure
[out]	dXco2_dT	derivative of mass fraction of CO2 in liqiud wrt temperature
[out]	dXco2_dX	derivative of mass fraction of CO2 in liqiud wrt salt mass fraction
[out]	Yh2o	mass fraction of H2O in gas (kg/kg)
[out]	dYh2og_dp	derivative of mass fraction of H2O in gas wrt pressure
[out]	dYh2o_dT	derivative of mass fraction of H2O in gas wrt temperature
[out]	dYh2o_dX	derivative of mass fraction of H2O in gas wrt salt mass fraction

Definition at line 524 of file PorousFlowBrineCO2.C.

Referenced by massFractions(), and totalMassFraction().

{
  Real co2_density, dco2_density_dp, dco2_density_dT;
  _co2_fp.rho_from_p_T(pressure, temperature, co2_density, dco2_density_dp, dco2_density_dT);

  // Mole fractions at equilibrium
  Real xco2, dxco2_dp, dxco2_dT, dxco2_dX, yh2o, dyh2o_dp, dyh2o_dT, dyh2o_dX;
  equilibriumMoleFractions(pressure,
                           temperature,
                           Xnacl,
                           xco2,
                           dxco2_dp,
                           dxco2_dT,
                           dxco2_dX,
                           yh2o,
                           dyh2o_dp,
                           dyh2o_dT,
                           dyh2o_dX);

  // The mass fraction of H2O in gas (assume no salt in gas phase) and derivatives
  // wrt p, T, and X
  Yh2o = yh2o * _Mh2o / (yh2o * _Mh2o + (1.0 - yh2o) * _Mco2);
  dYh2o_dp = _Mco2 * _Mh2o * dyh2o_dp / (yh2o * _Mh2o + (1.0 - yh2o) * _Mco2) /
             (yh2o * _Mh2o + (1.0 - yh2o) * _Mco2);
  dYh2o_dT = _Mco2 * _Mh2o * dyh2o_dT / (yh2o * _Mh2o + (1.0 - yh2o) * _Mco2) /
             (yh2o * _Mh2o + (1.0 - yh2o) * _Mco2);
  dYh2o_dX = dyh2o_dX * _Mh2o * _Mco2 / (yh2o * _Mh2o + (1.0 - yh2o) * _Mco2) /
             (yh2o * _Mh2o + (1.0 - yh2o) * _Mco2);

  // NaCl molality (mol/kg)
  const Real mnacl = Xnacl / (1.0 - Xnacl) / _Mnacl;
  const Real dmnacl_dX = 1.0 / (1.0 - Xnacl) / (1.0 - Xnacl) / _Mnacl;

  // The molality of CO2 in 1kg of H2O
  const Real mco2 = xco2 * (2.0 * mnacl + _invMh2o) / (1.0 - xco2);
  // The mass fraction of CO2 in brine is then
  const Real denominator = (1.0 + mnacl * _Mnacl + mco2 * _Mco2);
  Xco2 = mco2 * _Mco2 / denominator;

  // Derivatives of Xco2 wrt p, T and X
  const Real denominator2 = denominator * denominator;
  const Real dmco2_dp = dxco2_dp * (2.0 * mnacl + _invMh2o) / (1.0 - xco2) / (1.0 - xco2);
  dXco2_dp = (1.0 + mnacl * _Mnacl) * _Mco2 * dmco2_dp / denominator2;

  const Real dmco2_dT = dxco2_dT * (2.0 * mnacl + _invMh2o) / (1.0 - xco2) / (1.0 - xco2);
  dXco2_dT = (1.0 + mnacl * _Mnacl) * _Mco2 * dmco2_dT / denominator2;

  const Real dmco2_dX =
      (dxco2_dX * (2.0 * mnacl + _invMh2o) + 2.0 * (1.0 - xco2) * xco2 * dmnacl_dX) / (1.0 - xco2) /
      (1.0 - xco2);
  dXco2_dX = _Mco2 * ((1.0 + mnacl * _Mnacl) * dmco2_dX - dmnacl_dX * mco2 * _Mnacl) / denominator2;
}

equilibriumMoleFractions()

void PorousFlowBrineCO2::equilibriumMoleFractions	(	Real	pressure,
		Real	temperature,
		Real	Xnacl,
		Real &	xco2,
		Real &	dxco2_dp,
		Real &	dxco2_dT,
		Real &	dxco2_dX,
		Real &	yh2o,
		Real &	dyh2o_dp,
		Real &	dyh2o_dT,
		Real &	dyh2o_dX
	)		const

Mole fractions of CO2 in brine and water vapor in CO2 at equilibrium.

In the low temperature regime (T <= 99C), the mole fractions are calculated directly, while in the elevated temperature regime (T >= 109C), they are calculated iteratively. In the intermediate regime (99C < T < 109C), a cubic polynomial is used to smoothly connect the low and elevated temperature regimes.

Parameters

	pressure	phase pressure (Pa)
	temperature	phase temperature (K)
	Xnacl	NaCl mass fraction (kg/kg)
[out]	xco2	mole fraction of CO2 in liquid
[out]	dxco2_dp	derivative of mole fraction of CO2 in liquid wrt pressure
[out]	dxco2_dT	derivative of mole fraction of CO2 in liqiud wrt temperature
[out]	dxco2_dX	derivative of mole fraction of CO2 in liqiud wrt salt mass fraction
[out]	yh2o	mass fraction of mole in gas
[out]	dyh2og_dp	derivative of mole fraction of H2O in gas wrt pressure
[out]	dyh2o_dT	derivative of mole fraction of H2O in gas wrt temperature
[out]	dyh2o_dX	derivative of mole fraction of H2O in gas wrt salt mass fraction

Definition at line 970 of file PorousFlowBrineCO2.C.

Referenced by equilibriumMassFractions().

{
  // CO2 density and derivatives wrt pressure and temperature
  Real co2_density, dco2_density_dp, dco2_density_dT;
  _co2_fp.rho_from_p_T(pressure, temperature, co2_density, dco2_density_dp, dco2_density_dT);

  if (temperature <= _Tlower)
  {
    equilibriumMoleFractionsLowTemp(pressure,
                                    temperature,
                                    Xnacl,
                                    xco2,
                                    dxco2_dp,
                                    dxco2_dT,
                                    dxco2_dX,
                                    yh2o,
                                    dyh2o_dp,
                                    dyh2o_dT,
                                    dyh2o_dX);
  }
  else if (temperature > _Tlower && temperature < _Tupper)
  {
    // Cubic polynomial in this regime
    const Real Tint = (temperature - _Tlower) / 10.0;

    // Equilibrium mole fractions and derivatives at the lower temperature
    Real xco2_lower, dxco2_dT_lower, yh2o_lower, dyh2o_dT_lower;
    equilibriumMoleFractionsLowTemp(pressure,
                                    _Tlower,
                                    Xnacl,
                                    xco2_lower,
                                    dxco2_dp,
                                    dxco2_dT_lower,
                                    dxco2_dX,
                                    yh2o_lower,
                                    dyh2o_dp,
                                    dyh2o_dT_lower,
                                    dyh2o_dX);

    // Equilibrium mole fractions and derivatives at the upper temperature
    Real xco2_upper, yh2o_upper;
    Real co2_density_upper = _co2_fp.rho_from_p_T(pressure, _Tupper);

    solveEquilibriumMoleFractionHighTemp(
        pressure, _Tupper, Xnacl, co2_density_upper, xco2_upper, yh2o_upper);

    Real A, dA_dp, dA_dT, B, dB_dp, dB_dT, dB_dX;
    funcABHighTemp(pressure,
                   _Tupper,
                   Xnacl,
                   co2_density,
                   xco2_upper,
                   yh2o_upper,
                   A,
                   dA_dp,
                   dA_dT,
                   B,
                   dB_dp,
                   dB_dT,
                   dB_dX);

    const Real dyh2o_dT_upper =
        ((1.0 - B) * dA_dT + (A - 1.0) * A * dB_dT) / (1.0 - A * B) / (1.0 - A * B);
    const Real dxco2_dT_upper = dB_dT * (1.0 - yh2o_upper) - B * dyh2o_dT_upper;

    // The mole fractions in this regime are then found by interpolation
    Real dxco2_dT, dyh2o_dT;
    smoothCubicInterpolation(
        Tint, xco2_lower, dxco2_dT_lower, xco2_upper, dxco2_dT_upper, xco2, dxco2_dT);
    smoothCubicInterpolation(
        Tint, yh2o_lower, dyh2o_dT_lower, yh2o_upper, dyh2o_dT_upper, yh2o, dyh2o_dT);
  }
  else
  {
    // Equilibrium mole fractions solved using iteration in this regime
    solveEquilibriumMoleFractionHighTemp(pressure, temperature, Xnacl, co2_density, xco2, yh2o);

    // Can use these in funcABHighTemp() to get derivatives analyticall rather than by iteration
    Real A, dA_dp, dA_dT, B, dB_dp, dB_dT, dB_dX;
    funcABHighTemp(pressure,
                   temperature,
                   Xnacl,
                   co2_density,
                   xco2,
                   yh2o,
                   A,
                   dA_dp,
                   dA_dT,
                   B,
                   dB_dp,
                   dB_dT,
                   dB_dX);

    dyh2o_dp = ((1.0 - B) * dA_dp + (A - 1.0) * A * dB_dp) / (1.0 - A * B) / (1.0 - A * B);
    dxco2_dp = dB_dp * (1.0 - yh2o) - B * dyh2o_dp;

    dyh2o_dT = ((1.0 - B) * dA_dT + (A - 1.0) * A * dB_dT) / (1.0 - A * B) / (1.0 - A * B);
    dxco2_dT = dB_dT * (1.0 - yh2o) - B * dyh2o_dT;

    dyh2o_dX = ((A - 1.0) * A * dB_dX) / (1.0 - A * B) / (1.0 - A * B);
    dxco2_dX = dB_dX * (1.0 - yh2o) - B * dyh2o_dX;
  }
}

equilibriumMoleFractionsLowTemp()

void PorousFlowBrineCO2::equilibriumMoleFractionsLowTemp	(	Real	pressure,
		Real	temperature,
		Real	Xnacl,
		Real &	xco2,
		Real &	dxco2_dp,
		Real &	dxco2_dT,
		Real &	dxco2_dX,
		Real &	yh2o,
		Real &	dyh2o_dp,
		Real &	dyh2o_dT,
		Real &	dyh2o_dX
	)		const

Mole fractions of CO2 in brine and water vapor in CO2 at equilibrium in the low temperature regime (T <= 99C).

Parameters

	pressure	phase pressure (Pa)
	temperature	phase temperature (K)
	Xnacl	NaCl mass fraction (kg/kg)
[out]	xco2	mole fraction of CO2 in liquid
[out]	dxco2_dp	derivative of mole fraction of CO2 in liquid wrt pressure
[out]	dxco2_dT	derivative of mole fraction of CO2 in liqiud wrt temperature
[out]	dxco2_dX	derivative of mole fraction of CO2 in liqiud wrt salt mass fraction
[out]	yh2o	mass fraction of mole in gas
[out]	dyh2og_dp	derivative of mole fraction of H2O in gas wrt pressure
[out]	dyh2o_dT	derivative of mole fraction of H2O in gas wrt temperature
[out]	dyh2o_dX	derivative of mole fraction of H2O in gas wrt salt mass fraction

Definition at line 1085 of file PorousFlowBrineCO2.C.

Referenced by equilibriumMoleFractions().

{
  if (temperature > 373.15)
    mooseError(name(),
               ": equilibriumMoleFractionsLowTemp() is not valid for T > 373.15K. Use "
               "equilibriumMoleFractions() instead");

  // CO2 density and derivatives wrt pressure and temperature
  Real co2_density, dco2_density_dp, dco2_density_dT;
  _co2_fp.rho_from_p_T(pressure, temperature, co2_density, dco2_density_dp, dco2_density_dT);

  // Assume infinite dilution (yh20 = 0 and xco2 = 0) in low temperature regime
  Real A, dA_dp, dA_dT, B, dB_dp, dB_dT;
  funcABLowTemp(pressure,
                temperature,
                co2_density,
                dco2_density_dp,
                dco2_density_dT,
                A,
                dA_dp,
                dA_dT,
                B,
                dB_dp,
                dB_dT);

  // As the activity coefficient for CO2 in brine used in this regime isn't a 'true'
  // activity coefficient, we instead calculate the molality of CO2 in water, then
  // correct it for brine, and then calculate the mole fractions.
  // The mole fraction in pure water is
  const Real yh2ow = (1.0 - B) / (1.0 / A - B);
  const Real xco2w = B * (1.0 - yh2ow);

  // Molality of CO2 in pure water
  const Real mco2w = xco2w * _invMh2o / (1.0 - xco2w);
  // Molality of CO2 in brine is then calculated using gamma
  Real gamma, dgamma_dp, dgamma_dT, dgamma_dX;
  activityCoefficient(pressure, temperature, Xnacl, gamma, dgamma_dp, dgamma_dT, dgamma_dX);
  const Real mco2 = mco2w / gamma;

  // Need NaCl molality (mol/kg)
  const Real mnacl = Xnacl / (1.0 - Xnacl) / _Mnacl;
  const Real dmnacl_dX = 1.0 / (1.0 - Xnacl) / (1.0 - Xnacl) / _Mnacl;

  // Mole fractions of CO2 and H2O in liquid and gas phases
  const Real total_moles = 2.0 * mnacl + _invMh2o + mco2;
  xco2 = mco2 / total_moles;
  yh2o = A * (1.0 - xco2 - 2.0 * mnacl / total_moles);

  // The derivatives of the mole fractions wrt pressure
  const Real dyh2ow_dp =
      ((1.0 - B) * dA_dp + (A - 1.0) * A * dB_dp) / (1.0 - A * B) / (1.0 - A * B);
  const Real dxco2w_dp = dB_dp * (1.0 - yh2ow) - B * dyh2ow_dp;

  const Real dmco2w_dp = _invMh2o * dxco2w_dp / (1.0 - xco2w) / (1.0 - xco2w);
  const Real dmco2_dp = dmco2w_dp / gamma - mco2w * dgamma_dp / gamma / gamma;
  dxco2_dp = (2.0 * mnacl + _invMh2o) * dmco2_dp / total_moles / total_moles;

  dyh2o_dp = (1.0 - xco2 - 2.0 * mnacl / total_moles) * dA_dp - A * dxco2_dp +
             2.0 * A * mnacl * dmco2_dp / total_moles / total_moles;

  // The derivatives of the mole fractions wrt temperature
  const Real dyh2ow_dT =
      ((1.0 - B) * dA_dT + (A - 1.0) * A * dB_dT) / (1.0 - A * B) / (1.0 - A * B);
  const Real dxco2w_dT = dB_dT * (1.0 - yh2ow) - B * dyh2ow_dT;

  const Real dmco2w_dT = _invMh2o * dxco2w_dT / (1.0 - xco2w) / (1.0 - xco2w);
  const Real dmco2_dT = dmco2w_dT / gamma - mco2w * dgamma_dT / gamma / gamma;
  dxco2_dT = (2.0 * mnacl + _invMh2o) * dmco2_dT / total_moles / total_moles;

  dyh2o_dT = (1.0 - xco2 - 2.0 * mnacl / total_moles) * dA_dT - A * dxco2_dT +
             2.0 * A * mnacl * dmco2_dT / total_moles / total_moles;

  // The derivatives of the mole fractions wrt salt mass fraction
  const Real dmco2_dX = -mco2w * dgamma_dX / gamma / gamma;
  dxco2_dX =
      ((2.0 * mnacl + _invMh2o) * dmco2_dX - 2.0 * mco2 * dmnacl_dX) / total_moles / total_moles;
  dyh2o_dX =
      A * (2.0 * (mnacl * dmco2_dX - (mco2 + _invMh2o) * dmnacl_dX) / total_moles / total_moles -
           dxco2_dX);
}

execute()

void PorousFlowFluidStateFlash::execute ( )

inlinefinalinherited

Definition at line 37 of file PorousFlowFluidStateFlash.h.

{};

finalize()

void PorousFlowFluidStateFlash::finalize ( )

inlinefinalinherited

Definition at line 38 of file PorousFlowFluidStateFlash.h.

{};

fluidStateName()

std::string PorousFlowBrineCO2::fluidStateName ( ) const

overridevirtual

Name of FluidState.

Implements PorousFlowFluidStateBase.

Definition at line 83 of file PorousFlowBrineCO2.C.

{
  return "brine-co2";
}

fugacityCoefficientCO2HighTemp()

Real PorousFlowBrineCO2::fugacityCoefficientCO2HighTemp	(	Real	pressure,
		Real	temperature,
		Real	co2_density,
		Real	xco2,
		Real	yh2o
	)		const

Definition at line 762 of file PorousFlowBrineCO2.C.

Referenced by fugacityCoefficientsHighTemp().

{
  // Need pressure in bar
  const Real pbar = pressure * 1.0e-5;
  // Molar volume in cm^3/mol
  const Real V = _Mco2 / co2_density * 1.0e6;

  // Redlich-Kwong parameters
  const Real yco2 = 1.0 - yh2o;
  const Real xh2o = 1.0 - xco2;

  const Real aCO2 = 8.008e7 - 4.984e4 * temperature;
  const Real aH2O = 1.337e8 - 1.4e4 * temperature;
  const Real bCO2 = 28.25;
  const Real bH2O = 15.7;
  const Real KH2OCO2 = 1.427e-2 - 4.037e-4 * temperature;
  const Real KCO2H2O = 0.4228 - 7.422e-4 * temperature;
  const Real kH2OCO2 = KH2OCO2 * yh2o + KCO2H2O * yco2;
  const Real kCO2H2O = KCO2H2O * yh2o + KH2OCO2 * yco2;

  const Real aH2OCO2 = std::sqrt(aCO2 * aH2O) * (1.0 - kH2OCO2);
  const Real aCO2H2O = std::sqrt(aCO2 * aH2O) * (1.0 - kCO2H2O);

  const Real amix = yh2o * yh2o * aH2O + yh2o * yco2 * (aH2OCO2 + aCO2H2O) + yco2 * yco2 * aCO2;
  const Real bmix = yh2o * bH2O + yco2 * bCO2;

  const Real t15 = std::pow(temperature, 1.5);

  Real lnPhiCO2 = bCO2 / bmix * (pbar * V / (_Rbar * temperature) - 1.0) -
                  std::log(pbar * (V - bmix) / (_Rbar * temperature));

  Real term3 = (2.0 * yco2 * aCO2 + yh2o * (aH2OCO2 + aCO2H2O) -
                yh2o * yco2 * std::sqrt(aH2O * aCO2) * (kH2OCO2 - kCO2H2O) * (yh2o - yco2) +
                xh2o * xco2 * std::sqrt(aH2O * aCO2) * (kCO2H2O - kH2OCO2)) /
               amix;

  lnPhiCO2 += (term3 - bCO2 / bmix) * amix / (bmix * _Rbar * t15) * std::log(V / (V + bmix));

  return std::exp(lnPhiCO2);
}

fugacityCoefficientH2OHighTemp()

Real PorousFlowBrineCO2::fugacityCoefficientH2OHighTemp	(	Real	pressure,
		Real	temperature,
		Real	co2_density,
		Real	xco2,
		Real	yh2o
	)		const

Definition at line 719 of file PorousFlowBrineCO2.C.

Referenced by fugacityCoefficientsHighTemp().

{
  // Need pressure in bar
  const Real pbar = pressure * 1.0e-5;
  // Molar volume in cm^3/mol
  const Real V = _Mco2 / co2_density * 1.0e6;

  // Redlich-Kwong parameters
  const Real yco2 = 1.0 - yh2o;
  const Real xh2o = 1.0 - xco2;

  const Real aCO2 = 8.008e7 - 4.984e4 * temperature;
  const Real aH2O = 1.337e8 - 1.4e4 * temperature;
  const Real bCO2 = 28.25;
  const Real bH2O = 15.7;
  const Real KH2OCO2 = 1.427e-2 - 4.037e-4 * temperature;
  const Real KCO2H2O = 0.4228 - 7.422e-4 * temperature;
  const Real kH2OCO2 = KH2OCO2 * yh2o + KCO2H2O * yco2;
  const Real kCO2H2O = KCO2H2O * yh2o + KH2OCO2 * yco2;

  const Real aH2OCO2 = std::sqrt(aCO2 * aH2O) * (1.0 - kH2OCO2);
  const Real aCO2H2O = std::sqrt(aCO2 * aH2O) * (1.0 - kCO2H2O);

  const Real amix = yh2o * yh2o * aH2O + yh2o * yco2 * (aH2OCO2 + aCO2H2O) + yco2 * yco2 * aCO2;
  const Real bmix = yh2o * bH2O + yco2 * bCO2;

  const Real t15 = std::pow(temperature, 1.5);

  Real lnPhiH2O = bH2O / bmix * (pbar * V / (_Rbar * temperature) - 1.0) -
                  std::log(pbar * (V - bmix) / (_Rbar * temperature));
  Real term3 = (2.0 * yh2o * aH2O + yco2 * (aH2OCO2 + aCO2H2O) -
                yh2o * yco2 * std::sqrt(aH2O * aCO2) * (kH2OCO2 - kCO2H2O) * (yh2o - yco2) +
                xh2o * xco2 * std::sqrt(aH2O * aCO2) * (kH2OCO2 - kCO2H2O)) /
               amix;
  term3 -= bH2O / bmix;
  term3 *= amix / (bmix * _Rbar * t15) * std::log(V / (V + bmix));
  lnPhiH2O += term3;

  return std::exp(lnPhiH2O);
}

fugacityCoefficientsHighTemp() [1/2]

void PorousFlowBrineCO2::fugacityCoefficientsHighTemp	(	Real	pressure,
		Real	temperature,
		Real	co2_density,
		Real	xco2,
		Real	yh2o,
		Real &	fco2,
		Real &	fh2o
	)		const

Fugacity coefficients for H2O and CO2 at elevated temperatures (100C < T <= 300C).

Eq. (A8) from Spycher & Pruess (2010)

Parameters

	pressure	gas pressure (Pa)
	temperature	temperature (K)
	co2_density	CO2 density (kg/m^3)
	xco2	mole fraction of CO2 in liquid phase (-)
	yh2o	mole fraction of H2O in gas phase (-)
[out]	fco2	fugacity coefficient for CO2
[out]	dfco2_dp	derivative of fugacity coefficient wrt pressure
[out]	dfco2_dT	derivative of fugacity coefficient wrt temperature
[out]	fh2o	fugacity coefficient for H2O
[out]	dfh2o_dp	derivative of fugacity coefficient wrt pressure
[out]	dfh2o_dT	derivative of fugacity coefficient wrt temperature

Definition at line 663 of file PorousFlowBrineCO2.C.

Referenced by funcABHighTemp().

{
  if (temperature <= 373.15)
    mooseError(name(),
               ": fugacityCoefficientsHighTemp() is not valid for T <= 373.15K. Use "
               "fugacityCoefficientsLowTemp() instead");

  fh2o = fugacityCoefficientH2OHighTemp(pressure, temperature, co2_density, xco2, yh2o);
  fco2 = fugacityCoefficientCO2HighTemp(pressure, temperature, co2_density, xco2, yh2o);
}

fugacityCoefficientsHighTemp() [2/2]

void PorousFlowBrineCO2::fugacityCoefficientsHighTemp	(	Real	pressure,
		Real	temperature,
		Real	co2_density,
		Real	xco2,
		Real	yh2o,
		Real &	fco2,
		Real &	dfco2_dp,
		Real &	dfco2_dT,
		Real &	fh2o,
		Real &	dfh2o_dp,
		Real &	dfh2o_dT
	)		const

Definition at line 681 of file PorousFlowBrineCO2.C.

{
  if (temperature <= 373.15)
    mooseError(name(),
               ": fugacityCoefficientsHighTemp() is not valid for T <= 373.15K. Use "
               "fugacityCoefficientsLowTemp() instead");

  fh2o = fugacityCoefficientH2OHighTemp(pressure, temperature, co2_density, xco2, yh2o);
  fco2 = fugacityCoefficientCO2HighTemp(pressure, temperature, co2_density, xco2, yh2o);

  // Derivatives by finite difference
  const Real dp = 1.0e-2;
  const Real dT = 1.0e-4;

  Real fh2o2 = fugacityCoefficientH2OHighTemp(pressure + dp, temperature, co2_density, xco2, yh2o);
  Real fco22 = fugacityCoefficientCO2HighTemp(pressure + dp, temperature, xco2, co2_density, yh2o);

  dfh2o_dp = (fh2o2 - fh2o) / dp;
  dfco2_dp = (fco22 - fco2) / dp;

  fh2o2 = fugacityCoefficientH2OHighTemp(pressure, temperature + dT, co2_density, xco2, yh2o);
  fco22 = fugacityCoefficientCO2HighTemp(pressure, temperature + dT, co2_density, xco2, yh2o);

  dfh2o_dT = (fh2o2 - fh2o) / dT;
  dfco2_dT = (fco22 - fco2) / dT;
}

fugacityCoefficientsLowTemp()

void PorousFlowBrineCO2::fugacityCoefficientsLowTemp	(	Real	pressure,
		Real	temperature,
		Real	co2_density,
		Real	dco2_density_dp,
		Real	dco2_density_dT,
		Real &	fco2,
		Real &	dfco2_dp,
		Real &	dfco2_dT,
		Real &	fh2o,
		Real &	dfh2o_dp,
		Real &	dfh2o_dT
	)		const

Fugacity coefficients for H2O and CO2 for T <= 100C Eq.

(B7) from Spycher, Pruess and Ennis-King (2003)

Parameters

	pressure	gas pressure (Pa)
	temperature	temperature (K)
	co2_density	CO2 density (kg/m^3)
	dco2_density_dp	derivative of CO2 density wrt pressure
	dco2_density_dT	derivative of CO2 density wrt temperature
[out]	fco2	fugacity coefficient for CO2
[out]	dfco2_dp	derivative of fugacity coefficient wrt pressure
[out]	dfco2_dT	derivative of fugacity coefficient wrt temperature
[out]	fh2o	fugacity coefficient for H2O
[out]	dfh2o_dp	derivative of fugacity coefficient wrt pressure
[out]	dfh2o_dT	derivative of fugacity coefficient wrt temperature

Definition at line 588 of file PorousFlowBrineCO2.C.

Referenced by funcABLowTemp().

{
  if (temperature > 373.15)
    mooseError(name(),
               ": fugacityCoefficientsLowTemp() is not valid for T > 373.15K. Use "
               "fugacityCoefficientsHighTemp() instead");

  // Need pressure in bar
  const Real pbar = pressure * 1.0e-5;

  // Molar volume in cm^3/mol
  const Real V = _Mco2 / co2_density * 1.0e6;
  const Real dV_dp = -V / co2_density * dco2_density_dp;
  const Real dV_dT = -V / co2_density * dco2_density_dT;

  // Redlich-Kwong parameters
  const Real aCO2 = 7.54e7 - 4.13e4 * temperature;
  const Real daCO2_dT = -4.13e4;
  const Real bCO2 = 27.8;
  const Real aCO2H2O = 7.89e7;
  const Real bH2O = 18.18;

  const Real t15 = std::pow(temperature, 1.5);

  // The fugacity coefficients for H2O and CO2
  auto lnPhi = [V, aCO2, bCO2, t15, this](Real a, Real b) {
    return std::log(V / (V - bCO2)) + b / (V - bCO2) -
           2.0 * a / (_Rbar * t15 * bCO2) * std::log((V + bCO2) / V) +
           aCO2 * b / (_Rbar * t15 * bCO2 * bCO2) * (std::log((V + bCO2) / V) - bCO2 / (V + bCO2));
  };

  const Real lnPhiH2O = lnPhi(aCO2H2O, bH2O) - std::log(pbar * V / (_Rbar * temperature));
  const Real lnPhiCO2 = lnPhi(aCO2, bCO2) - std::log(pbar * V / (_Rbar * temperature));

  fh2o = std::exp(lnPhiH2O);
  fco2 = std::exp(lnPhiCO2);

  // The derivative of the fugacity coefficients wrt pressure
  auto dlnPhi_dV = [V, aCO2, bCO2, t15, this](Real a, Real b) {
    return (bCO2 * bCO2 - (bCO2 + b) * V) / V / (V - bCO2) / (V - bCO2) +
           (2.0 * a * (V + bCO2) - aCO2 * b) / (_Rbar * t15 * V * (V + bCO2) * (V + bCO2));
  };

  dfh2o_dp = (dlnPhi_dV(aCO2H2O, bH2O) * dV_dp - 1.0e-5 / pbar - dV_dp / V) * fh2o;
  dfco2_dp = (dlnPhi_dV(aCO2, bCO2) * dV_dp - 1.0e-5 / pbar - dV_dp / V) * fco2;

  // The derivative of the fugacity coefficient wrt temperature
  auto dlnPhi_dT = [V, aCO2, daCO2_dT, bCO2, t15, temperature, this](Real a, Real b, Real da_dT) {
    return (3.0 * bCO2 * a * std::log((V + bCO2) / V) +
            1.5 * aCO2 * b * (bCO2 / (V + bCO2) - std::log((V + bCO2) / V)) -
            (2.0 * da_dT * bCO2 * std::log((V + bCO2) / V) -
             daCO2_dT * b * (std::log((V + bCO2) / V) - bCO2 / (V + bCO2))) *
                temperature) /
           (temperature * t15 * _Rbar * bCO2 * bCO2);
  };

  dfh2o_dT = (dlnPhi_dT(aCO2H2O, bH2O, 0) + dlnPhi_dV(aCO2H2O, bH2O) * dV_dT - dV_dT / V +
              1.0 / temperature) *
             fh2o;
  dfco2_dT = (dlnPhi_dT(aCO2, bCO2, daCO2_dT) + dlnPhi_dV(aCO2, bCO2) * dV_dT - dV_dT / V +
              1.0 / temperature) *
             fco2;
}

funcABHighTemp() [1/2]

void PorousFlowBrineCO2::funcABHighTemp ( Real  pressure, Real  temperature, Real  Xnacl, Real  co2_density, Real  xco2, Real  yh2o, Real &  A, Real &  B  ) const

protected

The function A (Eq.

(11) of Spycher, Pruess and Ennis-King (2003) for T <= 100C, and Eqs. (10) and (17) of Spycher and Pruess (2010) for T > 100C)

Parameters

	pressure	gas pressure (Pa)
	temperature	fluid temperature (K)
	Xnacl	NaCl mass fraction (kg/kg)
	co2_density	CO2 density (kg/m^3)
	xco2	mole fraction of CO2 in liquid phase (-)
	yh2o	mole fraction of H2O in gas phase (-)
[out]	A	the function A
[out]	B	the function B

Definition at line 1242 of file PorousFlowBrineCO2.C.

Referenced by equilibriumMoleFractions(), funcABHighTemp(), and solveEquilibriumMoleFractionHighTemp().

{
  if (temperature <= 373.15)
    mooseError(name(),
               ": funcABHighTemp() is not valid for T <= 373.15K. Use funcABLowTemp() instead");

  // Pressure in bar
  const Real pbar = pressure * 1.0e-5;
  // Temperature in C
  const Real Tc = temperature - _T_c2k;

  // Reference pressure and partial molar volumes
  const Real pref = -1.9906e-1 + 2.0471e-3 * Tc + 1.0152e-4 * Tc * Tc - 1.4234e-6 * Tc * Tc * Tc +
                    1.4168e-8 * Tc * Tc * Tc * Tc;
  const Real vCO2 = 32.6 + 3.413e-2 * (Tc - 100.0);
  const Real vH2O = 18.1 + 3.137e-2 * (Tc - 100.0);

  const Real delta_pbar = pbar - pref;
  const Real Rt = _Rbar * temperature;

  // Equilibrium constants
  Real K0H2O, dK0H2O_dT, K0CO2, dK0CO2_dT;
  equilibriumConstantH2O(temperature, K0H2O, dK0H2O_dT);
  equilibriumConstantCO2(temperature, K0CO2, dK0CO2_dT);

  // Fugacity coefficients
  Real phiH2O, phiCO2;
  fugacityCoefficientsHighTemp(pressure, temperature, co2_density, xco2, yh2o, phiCO2, phiH2O);

  // Activity coefficients
  const Real gammaH2O = activityCoefficientH2O(temperature, xco2);
  const Real gammaCO2 = activityCoefficientCO2(temperature, xco2);

  // Activity coefficient for CO2 in brine
  Real gamma, dgamma_dT, dgamma_dX;
  activityCoefficientHighTemp(temperature, Xnacl, gamma, dgamma_dT, dgamma_dX);

  A = K0H2O * gammaH2O / (phiH2O * pbar) * std::exp(delta_pbar * vH2O / Rt);
  B = phiCO2 * pbar / (_invMh2o * K0CO2 * gamma * gammaCO2) * std::exp(-delta_pbar * vCO2 / Rt);
}

funcABHighTemp() [2/2]

void PorousFlowBrineCO2::funcABHighTemp ( Real  pressure, Real  temperature, Real  Xnacl, Real  co2_density, Real  xco2, Real  yh2o, Real &  A, Real &  dA_dp, Real &  dA_dT, Real &  B, Real &  dB_dp, Real &  dB_dT, Real &  dB_dX  ) const

protected

Definition at line 1291 of file PorousFlowBrineCO2.C.

{
  funcABHighTemp(pressure, temperature, Xnacl, co2_density, xco2, yh2o, A, B);

  // Use finite differences for derivatives in the high temperature regime
  const Real dp = 1.0e-2;
  const Real dT = 1.0e-6;
  const Real dX = 1.0e-8;

  Real A2, B2;
  funcABHighTemp(pressure + dp, temperature, Xnacl, co2_density, xco2, yh2o, A2, B2);
  dA_dp = (A2 - A) / dp;
  dB_dp = (B2 - B) / dp;

  funcABHighTemp(pressure, temperature + dT, Xnacl, co2_density, xco2, yh2o, A2, B2);
  dA_dT = (A2 - A) / dT;
  dB_dT = (B2 - B) / dT;

  funcABHighTemp(pressure, temperature, Xnacl + dX, co2_density, xco2, yh2o, A2, B2);
  dB_dX = (B2 - B) / dX;
}

funcABLowTemp()

void PorousFlowBrineCO2::funcABLowTemp ( Real  pressure, Real  temperature, Real  co2_density, Real  dco2_density_dp, Real  dco2_density_dT, Real &  A, Real &  dA_dp, Real &  dA_dT, Real &  B, Real &  dB_dp, Real &  dB_dT  ) const

protected

Definition at line 1177 of file PorousFlowBrineCO2.C.

Referenced by equilibriumMoleFractionsLowTemp().

{
  if (temperature > 373.15)
    mooseError(name(),
               ": funcABLowTemp() is not valid for T > 373.15K. Use funcABHighTemp() instead");

  // Pressure in bar
  const Real pbar = pressure * 1.0e-5;

  // Reference pressure and partial molar volumes
  const Real pref = 1.0;
  const Real vCO2 = 32.6;
  const Real vH2O = 18.1;

  const Real delta_pbar = pbar - pref;
  const Real Rt = _Rbar * temperature;

  // Equilibrium constants
  Real K0H2O, dK0H2O_dT, K0CO2, dK0CO2_dT;
  equilibriumConstantH2O(temperature, K0H2O, dK0H2O_dT);
  equilibriumConstantCO2(temperature, K0CO2, dK0CO2_dT);

  // Fugacity coefficients
  Real phiH2O, dphiH2O_dp, dphiH2O_dT;
  Real phiCO2, dphiCO2_dp, dphiCO2_dT;
  fugacityCoefficientsLowTemp(pressure,
                              temperature,
                              co2_density,
                              dco2_density_dp,
                              dco2_density_dT,
                              phiCO2,
                              dphiCO2_dp,
                              dphiCO2_dT,
                              phiH2O,
                              dphiH2O_dp,
                              dphiH2O_dT);

  A = K0H2O / (phiH2O * pbar) * std::exp(delta_pbar * vH2O / Rt);
  B = phiCO2 * pbar / (_invMh2o * K0CO2) * std::exp(-delta_pbar * vCO2 / Rt);

  dA_dp = (-1.0e-5 / pbar + 1.0e-5 * vH2O / Rt - dphiH2O_dp / phiH2O) * A;

  dB_dp = (1.0e-5 * phiCO2 + pbar * dphiCO2_dp - 1.0e-5 * vCO2 * pbar * phiCO2 / Rt) *
          std::exp(-delta_pbar * vCO2 / Rt) / (_invMh2o * K0CO2);

  dA_dT =
      (dK0H2O_dT - dphiH2O_dT * K0H2O / phiH2O - delta_pbar * vH2O * K0H2O / (Rt * temperature)) *
      std::exp(delta_pbar * vH2O / Rt) / (pbar * phiH2O);

  dB_dT = (-pbar * phiCO2 * dK0CO2_dT / K0CO2 + pbar * dphiCO2_dT +
           delta_pbar * vCO2 * pbar * phiCO2 / (Rt * temperature)) *
          std::exp(-delta_pbar * vCO2 / Rt) / (_invMh2o * K0CO2);
}

gasComponentIndex()

unsigned int PorousFlowFluidStateBase::gasComponentIndex ( ) const

inlineinherited

The index of the gas fluid component.

Returns

gas fluid component number

Definition at line 123 of file PorousFlowFluidStateBase.h.

{ return _gas_fluid_component; };

gasPhaseIndex()

unsigned int PorousFlowFluidStateBase::gasPhaseIndex ( ) const

inlineinherited

The index of the gas phase.

Returns

gas phase number

Definition at line 111 of file PorousFlowFluidStateBase.h.

{ return _gas_phase_number; };

gasProperties()

void PorousFlowBrineCO2::gasProperties	(	Real	pressure,
		Real	temperature,
		std::vector< FluidStateProperties > &	fsp
	)		const

Thermophysical properties of the gaseous state.

Parameters

	pressure	gas pressure (Pa)
	temperature	temperature (K)
[out]	FluidStateDensity	data structure

Definition at line 267 of file PorousFlowBrineCO2.C.

Referenced by thermophysicalProperties(), and totalMassFraction().

{
  FluidStateProperties & gas = fsp[_gas_phase_number];

  // Gas density, viscosity and enthalpy are approximated with pure CO2 - no correction due
  // to the small amount of water vapor is made
  Real co2_density, dco2_density_dp, dco2_density_dT;
  Real co2_viscosity, dco2_viscosity_dp, dco2_viscosity_dT;
  Real co2_enthalpy, dco2_enthalpy_dp, dco2_enthalpy_dT;
  _co2_fp.rho_mu_dpT(pressure,
                     temperature,
                     co2_density,
                     dco2_density_dp,
                     dco2_density_dT,
                     co2_viscosity,
                     dco2_viscosity_dp,
                     dco2_viscosity_dT);

  _co2_fp.h_from_p_T(pressure, temperature, co2_enthalpy, dco2_enthalpy_dp, dco2_enthalpy_dT);

  // Save the values to the FluidStateProperties object. Note that derivatives wrt z are 0
  gas.density = co2_density;
  gas.ddensity_dp = dco2_density_dp;
  gas.ddensity_dT = dco2_density_dT;
  gas.ddensity_dZ = 0.0;

  gas.viscosity = co2_viscosity;
  gas.dviscosity_dp = dco2_viscosity_dp;
  gas.dviscosity_dT = dco2_viscosity_dT;
  gas.dviscosity_dZ = 0.0;

  gas.enthalpy = co2_enthalpy;
  gas.denthalpy_dp = dco2_enthalpy_dp;
  gas.denthalpy_dT = dco2_enthalpy_dT;
  gas.denthalpy_dZ = 0.0;
}

henryConstant()

void PorousFlowBrineCO2::henryConstant	(	Real	temperature,
		Real	Xnacl,
		Real &	Kh,
		Real &	dKh_dT,
		Real &	dKh_dx
	)		const

Henry's constant of dissolution of gas phase CO2 in brine.

From Battistelli et al, A fluid property module for the TOUGH2 simulator for saline brines with non-condensible gas, Proc. Eighteenth Workshop on Geothermal Reservoir Engineering (1993)

Parameters

	temperature	fluid temperature (K)
	Xnacl	NaCl mass fraction (kg/kg)
[out]	Kh	Henry's constant (Pa)
[out]	dKh_dT	derivative of Henry's constant wrt temperature
[out]	dKh_dx	derivative of Henry's constant wrt salt mass fraction

Definition at line 1455 of file PorousFlowBrineCO2.C.

Referenced by enthalpyOfDissolutionGas().

{
  // Henry's constant for dissolution in water
  Real Kh_h2o, dKh_h2o_dT;
  _co2_fp.henryConstant_dT(temperature, Kh_h2o, dKh_h2o_dT);

  // The correction to salt is obtained through the salting out coefficient
  const std::vector<Real> b{1.19784e-1, -7.17823e-4, 4.93854e-6, -1.03826e-8, 1.08233e-11};

  // Need temperature in Celcius
  const Real Tc = temperature - _T_c2k;

  Real kb = 0.0;
  for (unsigned int i = 0; i < b.size(); ++i)
    kb += b[i] * MathUtils::pow(Tc, i);

  Real dkb_dT = 0.0;
  for (unsigned int i = 1; i < b.size(); ++i)
    dkb_dT += i * b[i] * MathUtils::pow(Tc, i - 1);

  // Need salt mass fraction in molality
  const Real xmol = Xnacl / (1.0 - Xnacl) / _Mnacl;
  const Real dxmol_dX = 1.0 / (1.0 - Xnacl) / (1.0 - Xnacl) / _Mnacl;
  // Henry's constant and its derivative wrt temperature and salt mass fraction
  Kh = Kh_h2o * std::pow(10.0, xmol * kb);
  dKh_dT = (xmol * std::log(10.0) * dkb_dT + dKh_h2o_dT / Kh_h2o) * Kh;
  dKh_dX = std::log(10.0) * kb * dxmol_dX * Kh;
}

initialize()

void PorousFlowFluidStateFlash::initialize ( )

inlinefinalinherited

Definition at line 36 of file PorousFlowFluidStateFlash.h.

{};

liquidProperties()

void PorousFlowBrineCO2::liquidProperties	(	Real	pressure,
		Real	temperature,
		Real	Xnacl,
		std::vector< FluidStateProperties > &	fsp
	)		const

Thermophysical properties of the liquid state.

Parameters

	pressure	liquid pressure (Pa)
	temperature	temperature (K)
	Xnacl	NaCl mass fraction (kg/kg)
[out]	FluidStateDensity	data structure

Definition at line 307 of file PorousFlowBrineCO2.C.

Referenced by thermophysicalProperties(), and totalMassFraction().

{
  FluidStateProperties & liquid = fsp[_aqueous_phase_number];

  // The liquid density includes the density increase due to dissolved CO2
  Real brine_density, dbrine_density_dp, dbrine_density_dT, dbrine_density_dX;
  _brine_fp.rho_dpTx(pressure,
                     temperature,
                     Xnacl,
                     brine_density,
                     dbrine_density_dp,
                     dbrine_density_dT,
                     dbrine_density_dX);

  // Mass fraction of CO2 in liquid phase
  const Real Xco2 = liquid.mass_fraction[_gas_fluid_component];
  const Real dXco2_dp = liquid.dmass_fraction_dp[_gas_fluid_component];
  const Real dXco2_dT = liquid.dmass_fraction_dT[_gas_fluid_component];
  const Real dXco2_dZ = liquid.dmass_fraction_dZ[_gas_fluid_component];
  const Real dXco2_dX = liquid.dmass_fraction_dX[_gas_fluid_component];

  // The liquid density
  Real co2_partial_density, dco2_partial_density_dT;
  partialDensityCO2(temperature, co2_partial_density, dco2_partial_density_dT);

  const Real liquid_density = 1.0 / (Xco2 / co2_partial_density + (1.0 - Xco2) / brine_density);

  const Real dliquid_density_dp =
      (dXco2_dp / brine_density + (1.0 - Xco2) * dbrine_density_dp / brine_density / brine_density -
       dXco2_dp / co2_partial_density) *
      liquid_density * liquid_density;

  const Real dliquid_density_dT =
      (dXco2_dT / brine_density + (1.0 - Xco2) * dbrine_density_dT / brine_density / brine_density -
       dXco2_dT / co2_partial_density +
       Xco2 * dco2_partial_density_dT / co2_partial_density / co2_partial_density) *
      liquid_density * liquid_density;

  const Real dliquid_density_dZ =
      (dXco2_dZ / brine_density - dXco2_dZ / co2_partial_density) * liquid_density * liquid_density;

  const Real dliquid_density_dX =
      (dXco2_dX / brine_density + (1.0 - Xco2) * dbrine_density_dX / brine_density / brine_density -
       dXco2_dX / co2_partial_density) *
      liquid_density * liquid_density;

  // Assume that liquid viscosity is just the brine viscosity
  Real liquid_viscosity, dliquid_viscosity_dp, dliquid_viscosity_dT, dliquid_viscosity_dX;
  _brine_fp.mu_dpTx(pressure,
                    temperature,
                    Xnacl,
                    liquid_viscosity,
                    dliquid_viscosity_dp,
                    dliquid_viscosity_dT,
                    dliquid_viscosity_dX);

  // Liquid enthalpy (including contribution due to the enthalpy of dissolution)
  Real brine_enthalpy, dbrine_enthalpy_dp, dbrine_enthalpy_dT, dbrine_enthalpy_dX;
  _brine_fp.h_dpTx(pressure,
                   temperature,
                   Xnacl,
                   brine_enthalpy,
                   dbrine_enthalpy_dp,
                   dbrine_enthalpy_dT,
                   dbrine_enthalpy_dX);

  // Enthalpy of CO2
  Real co2_enthalpy, dco2_enthalpy_dp, dco2_enthalpy_dT;
  _co2_fp.h_from_p_T(pressure, temperature, co2_enthalpy, dco2_enthalpy_dp, dco2_enthalpy_dT);

  // Enthalpy of dissolution
  Real hdis, dhdis_dT;
  enthalpyOfDissolution(temperature, hdis, dhdis_dT);

  const Real liquid_enthalpy = (1.0 - Xco2) * brine_enthalpy + Xco2 * (co2_enthalpy + hdis);
  const Real dliquid_enthalpy_dp = (1.0 - Xco2) * dbrine_enthalpy_dp + Xco2 * dco2_enthalpy_dp +
                                   dXco2_dp * (co2_enthalpy + hdis - brine_enthalpy);
  const Real dliquid_enthalpy_dT = (1.0 - Xco2) * dbrine_enthalpy_dT +
                                   Xco2 * (dco2_enthalpy_dT + dhdis_dT) +
                                   dXco2_dT * (co2_enthalpy + hdis - brine_enthalpy);
  const Real dliquid_enthalpy_dZ = dXco2_dZ * (co2_enthalpy + hdis - brine_enthalpy);
  const Real dliquid_enthalpy_dX =
      (1.0 - Xco2) * dbrine_enthalpy_dX + dXco2_dX * (co2_enthalpy + hdis - brine_enthalpy);

  // Save the values to the FluidStateProperties object
  liquid.density = liquid_density;
  liquid.ddensity_dp = dliquid_density_dp;
  liquid.ddensity_dT = dliquid_density_dT;
  liquid.ddensity_dZ = dliquid_density_dZ;
  liquid.ddensity_dX = dliquid_density_dX;

  liquid.viscosity = liquid_viscosity;
  liquid.dviscosity_dp = dliquid_viscosity_dp;
  liquid.dviscosity_dT = dliquid_viscosity_dT;
  liquid.dviscosity_dZ = 0.0;
  liquid.dviscosity_dX = dliquid_viscosity_dX;

  liquid.enthalpy = liquid_enthalpy;
  liquid.denthalpy_dp = dliquid_enthalpy_dp;
  liquid.denthalpy_dT = dliquid_enthalpy_dT;
  liquid.denthalpy_dZ = dliquid_enthalpy_dZ;
  liquid.denthalpy_dX = dliquid_enthalpy_dX;
}

massFractions()

void PorousFlowBrineCO2::massFractions	(	Real	pressure,
		Real	temperature,
		Real	Xnacl,
		Real	Z,
		FluidStatePhaseEnum &	phase_state,
		std::vector< FluidStateProperties > &	fsp
	)		const

Mass fractions of CO2 and H2O in both phases, as well as derivatives wrt PorousFlow variables.

Values depend on the phase state (liquid, gas or two phase)

Parameters

	pressure	phase pressure (Pa)
	temperature	phase temperature (K)
	Xnacl	NaCl mass fraction (kg/kg)
	Z	total mass fraction of CO2 component
[out]	PhaseStateEnum	current phase state
[out]	FluidStateMassFractions	data structure

Definition at line 159 of file PorousFlowBrineCO2.C.

Referenced by thermophysicalProperties().

{
  FluidStateProperties & liquid = fsp[_aqueous_phase_number];
  FluidStateProperties & gas = fsp[_gas_phase_number];

  // Equilibrium mass fraction of CO2 in liquid and H2O in gas phases
  Real Xco2, dXco2_dp, dXco2_dT, dXco2_dX, Yh2o, dYh2o_dp, dYh2o_dT, dYh2o_dX;
  equilibriumMassFractions(pressure,
                           temperature,
                           Xnacl,
                           Xco2,
                           dXco2_dp,
                           dXco2_dT,
                           dXco2_dX,
                           Yh2o,
                           dYh2o_dp,
                           dYh2o_dT,
                           dYh2o_dX);

  Real Yco2 = 1.0 - Yh2o;
  Real dYco2_dp = -dYh2o_dp;
  Real dYco2_dT = -dYh2o_dT;
  Real dYco2_dX = -dYh2o_dX;

  // Determine which phases are present based on the value of z
  phaseState(Z, Xco2, Yco2, phase_state);

  // The equilibrium mass fractions calculated above are only correct in the two phase
  // state. If only liquid or gas phases are present, the mass fractions are given by
  // the total mass fraction z
  Real Xh2o = 0.0;
  Real dXco2_dZ = 0.0, dYco2_dZ = 0.0;

  switch (phase_state)
  {
    case FluidStatePhaseEnum::LIQUID:
    {
      Xco2 = Z;
      Yco2 = 0.0;
      Xh2o = 1.0 - Z;
      Yh2o = 0.0;
      dXco2_dp = 0.0;
      dXco2_dT = 0.0;
      dXco2_dX = 0.0;
      dXco2_dZ = 1.0;
      dYco2_dp = 0.0;
      dYco2_dT = 0.0;
      dYco2_dX = 0.0;
      break;
    }

    case FluidStatePhaseEnum::GAS:
    {
      Xco2 = 0.0;
      Yco2 = Z;
      Yh2o = 1.0 - Z;
      dXco2_dp = 0.0;
      dXco2_dT = 0.0;
      dXco2_dX = 0.0;
      dYco2_dZ = 1.0;
      dYco2_dp = 0.0;
      dYco2_dT = 0.0;
      dYco2_dX = 0.0;
      break;
    }

    case FluidStatePhaseEnum::TWOPHASE:
    {
      // Keep equilibrium mass fractions
      Xh2o = 1.0 - Xco2;
      break;
    }
  }

  // Save the mass fractions in the FluidStateProperties object
  liquid.mass_fraction[_aqueous_fluid_component] = Xh2o;
  liquid.mass_fraction[_gas_fluid_component] = Xco2;
  liquid.mass_fraction[_salt_component] = Xnacl;
  gas.mass_fraction[_aqueous_fluid_component] = Yh2o;
  gas.mass_fraction[_gas_fluid_component] = Yco2;

  // Save the derivatives wrt PorousFlow variables
  liquid.dmass_fraction_dp[_aqueous_fluid_component] = -dXco2_dp;
  liquid.dmass_fraction_dp[_gas_fluid_component] = dXco2_dp;
  liquid.dmass_fraction_dT[_aqueous_fluid_component] = -dXco2_dT;
  liquid.dmass_fraction_dT[_gas_fluid_component] = dXco2_dT;
  liquid.dmass_fraction_dX[_aqueous_fluid_component] = -dXco2_dX;
  liquid.dmass_fraction_dX[_gas_fluid_component] = dXco2_dX;
  liquid.dmass_fraction_dX[_salt_component] = 1.0;
  liquid.dmass_fraction_dZ[_aqueous_fluid_component] = -dXco2_dZ;
  liquid.dmass_fraction_dZ[_gas_fluid_component] = dXco2_dZ;

  gas.dmass_fraction_dp[_aqueous_fluid_component] = -dYco2_dp;
  gas.dmass_fraction_dp[_gas_fluid_component] = dYco2_dp;
  gas.dmass_fraction_dT[_aqueous_fluid_component] = -dYco2_dT;
  gas.dmass_fraction_dT[_gas_fluid_component] = dYco2_dT;
  gas.dmass_fraction_dX[_aqueous_fluid_component] = -dYco2_dX;
  gas.dmass_fraction_dX[_gas_fluid_component] = dYco2_dX;
  gas.dmass_fraction_dZ[_aqueous_fluid_component] = -dYco2_dZ;
  gas.dmass_fraction_dZ[_gas_fluid_component] = dYco2_dZ;
}

numComponents()

unsigned int PorousFlowFluidStateBase::numComponents ( ) const

inlineinherited

The maximum number of components in this model.

Returns

number of components

Definition at line 99 of file PorousFlowFluidStateBase.h.

{ return _num_components; };

numPhases()

unsigned int PorousFlowFluidStateBase::numPhases ( ) const

inlineinherited

The maximum number of phases in this model.

Returns

number of phases

Definition at line 93 of file PorousFlowFluidStateBase.h.

Referenced by PorousFlowFluidState::PorousFlowFluidState().

{ return _num_phases; };

partialDensityCO2()

void PorousFlowBrineCO2::partialDensityCO2	(	Real	temperature,
		Real &	partial_density,
		Real &	dpartial_density_dT
	)		const

Partial density of dissolved CO2 From Garcia, Density of aqueous solutions of CO2, LBNL-49023 (2001)

Parameters

	temperature	fluid temperature (K)
[out]	partial	molar density (kg/m^3)
[out]	derivative	of partial molar density wrt temperature

Definition at line 1392 of file PorousFlowBrineCO2.C.

Referenced by liquidProperties(), and saturationTwoPhase().

{
  // This correlation uses temperature in C
  const Real Tc = temperature - _T_c2k;
  // The parial molar volume
  const Real V = 37.51 - 9.585e-2 * Tc + 8.74e-4 * Tc * Tc - 5.044e-7 * Tc * Tc * Tc;
  const Real dV_dT = -9.585e-2 + 1.748e-3 * Tc - 1.5132e-6 * Tc * Tc;

  partial_density = 1.0e6 * _Mco2 / V;
  dpartial_density_dT = -1.0e6 * _Mco2 * dV_dT / V / V;
}

phaseState()

void PorousFlowFluidStateFlash::phaseState ( Real  Zi, Real  Xi, Real  Yi, FluidStatePhaseEnum &  phase_state  ) const

protectedinherited

Determines the phase state gven the total mass fraction and equilibrium mass fractions.

Parameters

	Zi	total mass fraction
	Xi	equilibrium mass fraction in liquid
	Yi	equilibrium mass fraction in gas
[out]	phase_state	the phase state (gas, liquid, two phase)

Definition at line 29 of file PorousFlowFluidStateFlash.C.

Referenced by PorousFlowWaterNCG::massFractions(), and massFractions().

{
  if (Zi <= Xi)
  {
    // In this case, there is not enough component i to form a gas phase,
    // so only a liquid phase is present
    phase_state = FluidStatePhaseEnum::LIQUID;
  }
  else if (Zi > Xi && Zi < Yi)
  {
    // Two phases are present
    phase_state = FluidStatePhaseEnum::TWOPHASE;
  }
  else // (Zi >= Yi)
  {
    // In this case, there is not enough water to form a liquid
    // phase, so only a gas phase is present
    phase_state = FluidStatePhaseEnum::GAS;
  }
}

rachfordRice()

Real PorousFlowFluidStateFlash::rachfordRice ( Real  vf, std::vector< Real > &  Zi, std::vector< Real > &  Ki  ) const

inherited

Rachford-Rice equation for vapor fraction.

Can be solved analytically for two components in two phases, but must be solved iteratively using a root finding algorithm for more components. This equation has the nice property that it is monotonic in the interval [0,1], so that only a small number of iterations are typically required to find the root.

The Rachford-Rice equation can also be used to check whether the phase state is two phase, single phase gas, or single phase liquid. Evaluate f(v), the Rachford-Rice equation evaluated at the vapor mass fraction.

If f(0) < 0, then the mixture is below the bubble point, and only a single phase liquid can exist

If f(1) > 0, then the mixture is above the dew point, and only a single phase gas exists.

If f(0) >= 0 and f(1) <= 0, the mixture is between the bubble and dew points, and both gas and liquid phases exist.

Parameters

vf	vapor fraction
Zi	mass fractions
Ki	equilibrium constants

Returns

f(x)

Definition at line 54 of file PorousFlowFluidStateFlash.C.

Referenced by PorousFlowFluidStateFlash::vaporMassFraction().

{
  const std::size_t num_z = Zi.size();
  // Check that the sizes of the mass fractions and equilibrium constant vectors are correct
  if (Ki.size() != num_z + 1)
    mooseError("The number of mass fractions or equilibrium components passed to rachfordRice is "
               "not correct");

  Real f = 0.0;
  Real Z_total = 0.0;

  for (std::size_t i = 0; i < num_z; ++i)
  {
    f += Zi[i] * (Ki[i] - 1.0) / (1.0 + x * (Ki[i] - 1.0));
    Z_total += Zi[i];
  }

  // Add the last component (with total mass fraction = 1 - z_total)
  f += (1.0 - Z_total) * (Ki[num_z] - 1.0) / (1.0 + x * (Ki[num_z] - 1.0));

  return f;
}

rachfordRiceDeriv()

Real PorousFlowFluidStateFlash::rachfordRiceDeriv ( Real  vf, std::vector< Real > &  Zi, std::vector< Real > &  Ki  ) const

inherited

Derivative of Rachford-Rice equation wrt vapor fraction.

Has the nice property that it is strictly negative in the interval [0,1]

Parameters

vf	vapor fraction
Zi	mass fractions
Ki	equilibrium constants

Returns

f'(x)

Definition at line 80 of file PorousFlowFluidStateFlash.C.

Referenced by PorousFlowFluidStateFlash::vaporMassFraction().

{
  const std::size_t num_Z = Zi.size();
  // Check that the sizes of the mass fractions and equilibrium constant vectors are correct
  if (Ki.size() != num_Z + 1)
    mooseError("The number of mass fractions or equilibrium components passed to rachfordRice is "
               "not correct");

  Real df = 0.0;
  Real Z_total = 0.0;

  for (std::size_t i = 0; i < num_Z; ++i)
  {
    df -= Zi[i] * (Ki[i] - 1.0) * (Ki[i] - 1.0) / (1.0 + x * (Ki[i] - 1.0)) /
          (1.0 + x * (Ki[i] - 1.0));
    Z_total += Zi[i];
  }

  // Add the last component (with total mass fraction = 1 - z_total)
  df -= (1.0 - Z_total) * (Ki[num_Z] - 1.0) * (Ki[num_Z] - 1.0) / (1.0 + x * (Ki[num_Z] - 1.0)) /
        (1.0 + x * (Ki[num_Z] - 1.0));

  return df;
}

saltComponentIndex()

unsigned int PorousFlowBrineCO2::saltComponentIndex ( ) const

inline

The index of the salt component.

Returns

salt component number

Definition at line 357 of file PorousFlowBrineCO2.h.

{ return _salt_component; };

saturationTwoPhase()

void PorousFlowBrineCO2::saturationTwoPhase	(	Real	pressure,
		Real	temperature,
		Real	Xnacl,
		Real	Z,
		std::vector< FluidStateProperties > &	fsp
	)		const

Gas and liquid saturations for the two-phase region.

Parameters

	pressure	gas pressure (Pa)
	temperature	phase temperature (K)
	Xnacl	NaCl mass fraction (kg/kg)
	Z	total mass fraction of CO2 component
[out]	FluidStateSaturation	data structure

Definition at line 415 of file PorousFlowBrineCO2.C.

Referenced by thermophysicalProperties().

{
  FluidStateProperties & liquid = fsp[_aqueous_phase_number];
  FluidStateProperties & gas = fsp[_gas_phase_number];

  // Approximate liquid density as saturation isn't known yet
  Real brine_density, dbrine_density_dp, dbrine_density_dT, dbrine_density_dX;
  _brine_fp.rho_dpTx(pressure,
                     temperature,
                     Xnacl,
                     brine_density,
                     dbrine_density_dp,
                     dbrine_density_dT,
                     dbrine_density_dX);

  // Mass fraction of CO2 in liquid phase
  const Real Xco2 = liquid.mass_fraction[_gas_fluid_component];
  const Real dXco2_dp = liquid.dmass_fraction_dp[_gas_fluid_component];
  const Real dXco2_dT = liquid.dmass_fraction_dT[_gas_fluid_component];
  const Real dXco2_dX = liquid.dmass_fraction_dX[_gas_fluid_component];

  // The liquid density
  Real co2_partial_density, dco2_partial_density_dT;
  partialDensityCO2(temperature, co2_partial_density, dco2_partial_density_dT);

  const Real liquid_density = 1.0 / (Xco2 / co2_partial_density + (1.0 - Xco2) / brine_density);

  const Real dliquid_density_dp =
      (dXco2_dp / brine_density + (1.0 - Xco2) * dbrine_density_dp / brine_density / brine_density -
       dXco2_dp / co2_partial_density) *
      liquid_density * liquid_density;

  const Real dliquid_density_dT =
      (dXco2_dT / brine_density + (1.0 - Xco2) * dbrine_density_dT / brine_density / brine_density -
       dXco2_dT / co2_partial_density +
       Xco2 * dco2_partial_density_dT / co2_partial_density / co2_partial_density) *
      liquid_density * liquid_density;

  const Real dliquid_density_dX =
      (dXco2_dX / brine_density + (1.0 - Xco2) * dbrine_density_dX / brine_density / brine_density -
       dXco2_dX / co2_partial_density) *
      liquid_density * liquid_density;

  const Real Yco2 = gas.mass_fraction[_gas_fluid_component];
  const Real dYco2_dp = gas.dmass_fraction_dp[_gas_fluid_component];
  const Real dYco2_dT = gas.dmass_fraction_dT[_gas_fluid_component];
  const Real dYco2_dX = gas.dmass_fraction_dX[_gas_fluid_component];

  // Set mass equilibrium constants used in the calculation of vapor mass fraction
  const Real K0 = Yco2 / Xco2;
  const Real K1 = (1.0 - Yco2) / (1.0 - Xco2);
  const Real vapor_mass_fraction = vaporMassFraction(Z, K0, K1);

  // The gas saturation in the two phase case
  gas.saturation = vapor_mass_fraction * liquid_density /
                   (gas.density + vapor_mass_fraction * (liquid_density - gas.density));

  const Real dv_dZ = (K1 - K0) / ((K0 - 1.0) * (K1 - 1.0));
  const Real denominator = (gas.density + vapor_mass_fraction * (liquid_density - gas.density)) *
                           (gas.density + vapor_mass_fraction * (liquid_density - gas.density));

  const Real ds_dZ = gas.density * liquid_density * dv_dZ / denominator;

  const Real dK0_dp = (Xco2 * dYco2_dp - Yco2 * dXco2_dp) / Xco2 / Xco2;
  const Real dK0_dT = (Xco2 * dYco2_dT - Yco2 * dXco2_dT) / Xco2 / Xco2;
  const Real dK0_dX = (Xco2 * dYco2_dX - Yco2 * dXco2_dX) / Xco2 / Xco2;

  const Real dK1_dp =
      ((1.0 - Yco2) * dXco2_dp - (1.0 - Xco2) * dYco2_dp) / (1.0 - Xco2) / (1.0 - Xco2);
  const Real dK1_dT =
      ((1.0 - Yco2) * dXco2_dT - (1.0 - Xco2) * dYco2_dT) / (1.0 - Xco2) / (1.0 - Xco2);
  const Real dK1_dX =
      ((1.0 - Yco2) * dXco2_dX - (1.0 - Xco2) * dYco2_dX) / (1.0 - Xco2) / (1.0 - Xco2);

  const Real dv_dp =
      Z * dK1_dp / (K1 - 1.0) / (K1 - 1.0) + (1.0 - Z) * dK0_dp / (K0 - 1.0) / (K0 - 1.0);

  Real ds_dp = gas.density * liquid_density * dv_dp +
               vapor_mass_fraction * (1.0 - vapor_mass_fraction) *
                   (gas.density * dliquid_density_dp - gas.ddensity_dp * liquid_density);
  ds_dp /= denominator;

  const Real dv_dT =
      Z * dK1_dT / (K1 - 1.0) / (K1 - 1.0) + (1.0 - Z) * dK0_dT / (K0 - 1.0) / (K0 - 1.0);

  Real ds_dT = gas.density * liquid_density * dv_dT +
               vapor_mass_fraction * (1.0 - vapor_mass_fraction) *
                   (gas.density * dliquid_density_dT - gas.ddensity_dT * liquid_density);
  ds_dT /= denominator;

  const Real dv_dX =
      Z * dK1_dX / (K1 - 1.0) / (K1 - 1.0) + (1.0 - Z) * dK0_dX / (K0 - 1.0) / (K0 - 1.0);

  Real ds_dX = gas.density * liquid_density * dv_dX + vapor_mass_fraction *
                                                          (1.0 - vapor_mass_fraction) *
                                                          (gas.density * dliquid_density_dX);
  ds_dX /= denominator;

  gas.dsaturation_dp = ds_dp;
  gas.dsaturation_dT = ds_dT;
  gas.dsaturation_dZ = ds_dZ;
  gas.dsaturation_dX = ds_dX;
}

smoothCubicInterpolation()

void PorousFlowBrineCO2::smoothCubicInterpolation ( Real  temperature, Real  f0, Real  df0, Real  f1, Real  df1, Real &  value, Real &  deriv  ) const

protected

Cubic function to smoothly interpolate between the low temperature and elevated temperature models for 99C < T < 109C.

Parameters

	temperature	temperature (K)
	f0	function value at T = 372K (99C)
	df0	derivative of function at T = 372K (99C)
	f1	function value at T = 382K (109C)
	df1	derivative of function at T = 382K (109C)
[out]	value	value at the given temperature
[out]	deriv	derivative at the given temperature

Definition at line 1522 of file PorousFlowBrineCO2.C.

Referenced by equilibriumMoleFractions().

{
  // Coefficients of cubic polynomial
  const Real dT = _Tupper - _Tlower;

  const Real a = f0;
  const Real b = df0 * dT;
  const Real c = 3.0 * (f1 - f0) - (2.0 * df0 + df1) * dT;
  const Real d = 2.0 * (f0 - f1) + (df0 + df1) * dT;

  const Real t2 = temperature * temperature;
  const Real t3 = temperature * t2;

  value = a + b * temperature + c * t2 + d * t3;
  deriv = b + 2.0 * c * temperature + 3.0 * d * t2;
}

solveEquilibriumMoleFractionHighTemp()

void PorousFlowBrineCO2::solveEquilibriumMoleFractionHighTemp	(	Real	pressure,
		Real	temperature,
		Real	Xnacl,
		Real	co2_density,
		Real &	xco2,
		Real &	yh2o
	)		const

Function to solve for yh2o and xco2 iteratively in the elevated temperature regime (T > 100C)

Parameters

	pressure	gas pressure (Pa)
	temperature	fluid temperature (K)
	Xnacl	NaCl mass fraction (kg/kg)
	co2_density	CO2 density (kg/m^3)
[out]	xco2	mole fraction of CO2 in liquid phase (-)
[out]	yh2o	mole fraction of H2O in gas phase (-)

Definition at line 1326 of file PorousFlowBrineCO2.C.

Referenced by equilibriumMoleFractions().

{
  // Initial guess for yh2o and xco2 (from Spycher and Pruess (2010))
  Real y = _brine_fp.vaporPressure(temperature, 0.0) / pressure;
  Real x = 0.009;

  // Need salt mass fraction in molality
  const Real mnacl = Xnacl / (1.0 - Xnacl) / _Mnacl;

  // If y > 1, then just use y = 1, x = 0 (only a gas phase)
  if (y >= 1.0)
  {
    y = 1.0;
    x = 0.0;
  }
  else
  {
    // Residual function for Newton-Raphson
    auto fy = [mnacl, this](Real y, Real A, Real B) {
      return y -
             (1.0 - B) * _invMh2o / ((1.0 / A - B) * (2.0 * mnacl + _invMh2o) + 2.0 * mnacl * B);
    };

    // Derivative of fy wrt y
    auto dfy = [mnacl, this](Real A, Real B, Real dA, Real dB) {
      const Real denominator = (1.0 / A - B) * (2.0 * mnacl + _invMh2o) + 2.0 * mnacl * B;
      return 1.0 + _invMh2o * dB / denominator +
             (1.0 - B) * _invMh2o *
                 (2.0 * mnacl * dB - (2.0 * mnacl + _invMh2o) * (dB + dA / A / A)) / denominator /
                 denominator;
    };

    Real A, B;
    Real dA, dB;
    const Real dy = 1.0e-8;

    // Solve for yh2o using Newton-Raphson method
    unsigned int iter = 0;
    const Real tol = 1.0e-12;
    const unsigned int max_its = 10;
    funcABHighTemp(pressure, temperature, Xnacl, co2_density, x, y, A, B);

    while (std::abs(fy(y, A, B)) > tol)
    {
      funcABHighTemp(pressure, temperature, Xnacl, co2_density, x, y, A, B);
      // Finite difference derivatives of A and B wrt y
      funcABHighTemp(pressure, temperature, Xnacl, co2_density, x, y + dy, dA, dB);
      dA = (dA - A) / dy;
      dB = (dB - B) / dy;

      y = y - fy(y, A, B) / dfy(A, B, dA, dB);

      x = B * (1.0 - y);

      // Break if not converged and just use the value
      if (iter > max_its)
        break;
    }
  }

  yh2o = y;
  xco2 = x;
}

thermophysicalProperties()

void PorousFlowBrineCO2::thermophysicalProperties ( Real  pressure, Real  temperature, Real  Xnacl, Real  Z, unsigned int  qp, std::vector< FluidStateProperties > &  fsp  ) const

overridevirtual

Determines the complete thermophysical state of the system for a given set of primary variables.

Parameters

	pressure	gas phase pressure (Pa)
	temperature	fluid temperature (K)
	Xnacl	mass fraction of NaCl
	Z	total mass fraction of fluid component
	qp	quadpoint index
[out]	fsp	the FluidStateProperties struct containing all properties

Implements PorousFlowFluidStateBase.

Definition at line 89 of file PorousFlowBrineCO2.C.

{
  FluidStateProperties & liquid = fsp[_aqueous_phase_number];
  FluidStateProperties & gas = fsp[_gas_phase_number];

  // Check whether the input temperature is within the region of validity
  checkVariables(pressure, temperature);

  // Clear all of the FluidStateProperties data
  clearFluidStateProperties(fsp);

  FluidStatePhaseEnum phase_state;
  massFractions(pressure, temperature, Xnacl, Z, phase_state, fsp);

  switch (phase_state)
  {
    case FluidStatePhaseEnum::GAS:
    {
      // Set the gas saturations
      gas.saturation = 1.0;

      // Calculate gas properties
      gasProperties(pressure, temperature, fsp);

      break;
    }

    case FluidStatePhaseEnum::LIQUID:
    {
      // Calculate the liquid properties
      Real liquid_pressure = pressure - _pc.capillaryPressure(1.0, qp);
      liquidProperties(liquid_pressure, temperature, Xnacl, fsp);

      break;
    }

    case FluidStatePhaseEnum::TWOPHASE:
    {
      // Calculate the gas properties
      gasProperties(pressure, temperature, fsp);

      // Calculate the saturation
      saturationTwoPhase(pressure, temperature, Xnacl, Z, fsp);

      // Calculate the liquid properties
      Real liquid_pressure = pressure - _pc.capillaryPressure(1.0 - gas.saturation, qp);
      liquidProperties(liquid_pressure, temperature, Xnacl, fsp);

      break;
    }
  }

  // Liquid saturations can now be set
  liquid.saturation = 1.0 - gas.saturation;
  liquid.dsaturation_dp = -gas.dsaturation_dp;
  liquid.dsaturation_dT = -gas.dsaturation_dT;
  liquid.dsaturation_dX = -gas.dsaturation_dX;
  liquid.dsaturation_dZ = -gas.dsaturation_dZ;

  // Save pressures to FluidStateProperties object
  gas.pressure = pressure;
  liquid.pressure = pressure - _pc.capillaryPressure(liquid.saturation, qp);
}

totalMassFraction()

Real PorousFlowBrineCO2::totalMassFraction ( Real  pressure, Real  temperature, Real  Xnacl, Real  saturation, unsigned int  qp  ) const

overridevirtual

Total mass fraction of fluid component summed over all phases in the two-phase state for a specified gas saturation.

Parameters

pressure	gas pressure (Pa)
temperature	temperature (K)
Xnacl	NaCl mass fraction (kg/kg)
saturation	gas saturation (-)
qp	quadpoint index

Returns

total mass fraction Z (-)

Implements PorousFlowFluidStateBase.

Definition at line 1407 of file PorousFlowBrineCO2.C.

{
  // Check whether the input pressure and temperature are within the region of validity
  checkVariables(pressure, temperature);

  // FluidStateProperties data structure
  std::vector<FluidStateProperties> fsp(_num_phases, FluidStateProperties(_num_components));
  FluidStateProperties & liquid = fsp[_aqueous_phase_number];
  FluidStateProperties & gas = fsp[_gas_phase_number];

  // Calculate equilibrium mass fractions in the two-phase state
  Real Xco2, dXco2_dp, dXco2_dT, dXco2_dX, Yh2o, dYh2o_dp, dYh2o_dT, dYh2o_dX;
  equilibriumMassFractions(pressure,
                           temperature,
                           Xnacl,
                           Xco2,
                           dXco2_dp,
                           dXco2_dT,
                           dXco2_dX,
                           Yh2o,
                           dYh2o_dp,
                           dYh2o_dT,
                           dYh2o_dX);

  // Save the mass fractions in the FluidStateMassFractions object
  const Real Yco2 = 1.0 - Yh2o;
  liquid.mass_fraction[_aqueous_fluid_component] = 1.0 - Xco2;
  liquid.mass_fraction[_gas_fluid_component] = Xco2;
  gas.mass_fraction[_aqueous_fluid_component] = Yh2o;
  gas.mass_fraction[_gas_fluid_component] = Yco2;

  // Gas properties
  gasProperties(pressure, temperature, fsp);

  // Liquid properties
  const Real liquid_saturation = 1.0 - saturation;
  const Real liquid_pressure = pressure - _pc.capillaryPressure(liquid_saturation, qp);
  liquidProperties(liquid_pressure, temperature, Xnacl, fsp);

  // The total mass fraction of ncg (z) can now be calculated
  const Real Z = (saturation * gas.density * Yco2 + liquid_saturation * liquid.density * Xco2) /
                 (saturation * gas.density + liquid_saturation * liquid.density);

  return Z;
}

vaporMassFraction() [1/2]

Real PorousFlowFluidStateFlash::vaporMassFraction ( Real  Z0, Real  K0, Real  K1  ) const

inherited

Solves Rachford-Rice equation to provide vapor mass fraction.

For two components, the analytical solution is used, while for cases with more than two components, a Newton-Raphson iterative solution is calculated.

Parameters

Zi	total mass fraction(s)
Ki	equilibrium constant(s)

Returns

vapor mass fraction

Definition at line 108 of file PorousFlowFluidStateFlash.C.

Referenced by PorousFlowWaterNCG::saturationTwoPhase(), saturationTwoPhase(), and PorousFlowFluidStateFlash::vaporMassFraction().

{
  return (Z0 * (K1 - K0) - (K1 - 1.0)) / ((K0 - 1.0) * (K1 - 1.0));
}

vaporMassFraction() [2/2]

Real PorousFlowFluidStateFlash::vaporMassFraction ( std::vector< Real > &  Zi, std::vector< Real > &  Ki  ) const

inherited

Definition at line 114 of file PorousFlowFluidStateFlash.C.

{
  // Check that the sizes of the mass fractions and equilibrium constant vectors are correct
  if (Ki.size() != Zi.size() + 1)
    mooseError("The number of mass fractions or equilibrium components passed to rachfordRice is "
               "not correct");
  Real v;

  // If there are only two components, an analytical solution is possible
  if (Ki.size() == 2)
    v = vaporMassFraction(Zi[0], Ki[0], Ki[1]);
  else
  {
    // More than two components - solve the Rachford-Rice equation using
    // Newton-Raphson method
    // Initial guess for vapor mass fraction
    Real v0 = 0.5;
    unsigned int iter = 0;

    while (std::abs(rachfordRice(v0, Zi, Ki)) > _nr_tol)
    {
      v0 = v0 - rachfordRice(v0, Zi, Ki) / rachfordRiceDeriv(v0, Zi, Ki);
      iter++;

      if (iter > _nr_max_its)
        break;
    }
    v = v0;
  }
  return v;
}

Member Data Documentation

_aqueous_fluid_component

const unsigned int PorousFlowFluidStateBase::_aqueous_fluid_component

protectedinherited

Fluid component number of the aqueous component.

Definition at line 184 of file PorousFlowFluidStateBase.h.

Referenced by PorousFlowFluidStateBase::aqueousComponentIndex(), PorousFlowWaterNCG::massFractions(), massFractions(), PorousFlowBrineCO2(), PorousFlowWaterNCG::PorousFlowWaterNCG(), PorousFlowWaterNCG::totalMassFraction(), and totalMassFraction().

_aqueous_phase_number

const unsigned int PorousFlowFluidStateBase::_aqueous_phase_number

protectedinherited

Phase number of the aqueous phase.

Definition at line 180 of file PorousFlowFluidStateBase.h.

Referenced by PorousFlowFluidStateBase::aqueousPhaseIndex(), PorousFlowWaterNCG::gasProperties(), PorousFlowWaterNCG::liquidProperties(), liquidProperties(), PorousFlowWaterNCG::massFractions(), massFractions(), PorousFlowBrineCO2(), PorousFlowWaterNCG::PorousFlowWaterNCG(), PorousFlowWaterNCG::saturationTwoPhase(), saturationTwoPhase(), PorousFlowWaterNCG::thermophysicalProperties(), thermophysicalProperties(), PorousFlowWaterNCG::totalMassFraction(), and totalMassFraction().

_brine_fp

const BrineFluidProperties& PorousFlowBrineCO2::_brine_fp

protected

Fluid properties UserObject for water.

Definition at line 522 of file PorousFlowBrineCO2.h.

Referenced by liquidProperties(), PorousFlowBrineCO2(), saturationTwoPhase(), and solveEquilibriumMoleFractionHighTemp().

_co2_fp

const SinglePhaseFluidProperties& PorousFlowBrineCO2::_co2_fp

protected

Fluid properties UserObject for the CO2.

Definition at line 524 of file PorousFlowBrineCO2.h.

Referenced by equilibriumMassFractions(), equilibriumMoleFractions(), equilibriumMoleFractionsLowTemp(), gasProperties(), henryConstant(), liquidProperties(), and PorousFlowBrineCO2().

_gas_fluid_component

unsigned int PorousFlowFluidStateBase::_gas_fluid_component

protectedinherited

Fluid component number of the gas phase.

Definition at line 186 of file PorousFlowFluidStateBase.h.

Referenced by PorousFlowFluidStateBase::gasComponentIndex(), PorousFlowWaterNCG::gasProperties(), PorousFlowWaterNCG::liquidProperties(), liquidProperties(), PorousFlowWaterNCG::massFractions(), massFractions(), PorousFlowBrineCO2(), PorousFlowWaterNCG::PorousFlowWaterNCG(), PorousFlowWaterNCG::saturationTwoPhase(), saturationTwoPhase(), PorousFlowWaterNCG::totalMassFraction(), and totalMassFraction().

_gas_phase_number

unsigned int PorousFlowFluidStateBase::_gas_phase_number

protectedinherited

Phase number of the gas phase.

Definition at line 182 of file PorousFlowFluidStateBase.h.

Referenced by PorousFlowFluidStateBase::gasPhaseIndex(), PorousFlowWaterNCG::gasProperties(), gasProperties(), PorousFlowWaterNCG::massFractions(), massFractions(), PorousFlowBrineCO2(), PorousFlowWaterNCG::PorousFlowWaterNCG(), PorousFlowWaterNCG::saturationTwoPhase(), saturationTwoPhase(), PorousFlowWaterNCG::thermophysicalProperties(), thermophysicalProperties(), PorousFlowWaterNCG::totalMassFraction(), and totalMassFraction().

_invMh2o

const Real PorousFlowBrineCO2::_invMh2o

protected

Inverse of molar mass of H2O (mol/kg)

Definition at line 530 of file PorousFlowBrineCO2.h.

Referenced by activityCoefficientHighTemp(), equilibriumMassFractions(), equilibriumMoleFractionsLowTemp(), funcABHighTemp(), funcABLowTemp(), and solveEquilibriumMoleFractionHighTemp().

_Mco2

const Real PorousFlowBrineCO2::_Mco2

protected

Molar mass of CO2 (kg/mol)

Definition at line 532 of file PorousFlowBrineCO2.h.

Referenced by enthalpyOfDissolution(), enthalpyOfDissolutionGas(), equilibriumMassFractions(), fugacityCoefficientCO2HighTemp(), fugacityCoefficientH2OHighTemp(), fugacityCoefficientsLowTemp(), and partialDensityCO2().

_Mh2o

const Real PorousFlowBrineCO2::_Mh2o

protected

Molar mass of water (kg/mol)

Definition at line 528 of file PorousFlowBrineCO2.h.

Referenced by equilibriumMassFractions().

_Mnacl

const Real PorousFlowBrineCO2::_Mnacl

protected

Molar mass of NaCL.

Definition at line 534 of file PorousFlowBrineCO2.h.

Referenced by activityCoefficient(), activityCoefficientHighTemp(), equilibriumMassFractions(), equilibriumMoleFractionsLowTemp(), henryConstant(), and solveEquilibriumMoleFractionHighTemp().

_nr_max_its

const Real PorousFlowFluidStateBase::_nr_max_its

protectedinherited

Maximum number of iterations for the Newton-Raphson iterations.

Definition at line 194 of file PorousFlowFluidStateBase.h.

_nr_tol

const Real PorousFlowFluidStateBase::_nr_tol

protectedinherited

Tolerance for Newton-Raphson iterations.

Definition at line 196 of file PorousFlowFluidStateBase.h.

_num_components

unsigned int PorousFlowFluidStateBase::_num_components

protectedinherited

Number of components.

Definition at line 178 of file PorousFlowFluidStateBase.h.

Referenced by PorousFlowFluidStateBase::clearFluidStateProperties(), PorousFlowFluidStateBase::numComponents(), PorousFlowBrineCO2(), PorousFlowWaterNCG::PorousFlowWaterNCG(), PorousFlowWaterNCG::totalMassFraction(), and totalMassFraction().

_num_phases

unsigned int PorousFlowFluidStateBase::_num_phases

protectedinherited

Number of phases.

Definition at line 176 of file PorousFlowFluidStateBase.h.

Referenced by PorousFlowFluidStateBase::numPhases(), PorousFlowBrineCO2(), PorousFlowWaterNCG::PorousFlowWaterNCG(), PorousFlowWaterNCG::totalMassFraction(), and totalMassFraction().

_pc

const PorousFlowCapillaryPressure& PorousFlowFluidStateBase::_pc

protectedinherited

Capillary pressure UserObject.

Definition at line 198 of file PorousFlowFluidStateBase.h.

Referenced by PorousFlowWaterNCG::thermophysicalProperties(), thermophysicalProperties(), PorousFlowWaterNCG::totalMassFraction(), and totalMassFraction().

_R

const Real PorousFlowFluidStateBase::_R

protectedinherited

Universal gas constant (J/mol/K)

Definition at line 190 of file PorousFlowFluidStateBase.h.

Referenced by PorousFlowWaterNCG::enthalpyOfDissolution(), and enthalpyOfDissolutionGas().

_Rbar

const Real PorousFlowBrineCO2::_Rbar

protected

Molar gas constant in bar cm^3 /(K mol)

Definition at line 536 of file PorousFlowBrineCO2.h.

Referenced by fugacityCoefficientCO2HighTemp(), fugacityCoefficientH2OHighTemp(), fugacityCoefficientsLowTemp(), funcABHighTemp(), and funcABLowTemp().

_salt_component

const unsigned int PorousFlowBrineCO2::_salt_component

protected

Salt component index.

Definition at line 520 of file PorousFlowBrineCO2.h.

Referenced by massFractions(), PorousFlowBrineCO2(), and saltComponentIndex().

_T_c2k

const Real PorousFlowFluidStateBase::_T_c2k

protectedinherited

Conversion from C to K.

Definition at line 192 of file PorousFlowFluidStateBase.h.

Referenced by equilibriumConstantCO2(), equilibriumConstantH2O(), funcABHighTemp(), henryConstant(), and partialDensityCO2().

_Tlower

const Real PorousFlowBrineCO2::_Tlower

protected

Temperature below which the Spycher, Pruess & Ennis-King (2003) model is used (K)

Definition at line 538 of file PorousFlowBrineCO2.h.

Referenced by equilibriumMoleFractions(), and smoothCubicInterpolation().

_Tupper

const Real PorousFlowBrineCO2::_Tupper

protected

Temperature above which the Spycher & Pruess (2010) model is used (K)

Definition at line 540 of file PorousFlowBrineCO2.h.

Referenced by equilibriumMoleFractions(), and smoothCubicInterpolation().

_water_fp

const SinglePhaseFluidProperties& PorousFlowBrineCO2::_water_fp

protected

Fluid properties UserObject for H20.

Definition at line 526 of file PorousFlowBrineCO2.h.

---

The documentation for this class was generated from the following files:

• porous_flow/include/userobjects/PorousFlowBrineCO2.h
• porous_flow/src/userobjects/PorousFlowBrineCO2.C