Cantera  3.1.0a1
Loading...
Searching...
No Matches
MolalityVPSSTP Class Reference

MolalityVPSSTP is a derived class of ThermoPhase that handles variable pressure standard state methods for calculating thermodynamic properties that are further based on molality-scaled activities. More...

#include <MolalityVPSSTP.h>

Inheritance diagram for MolalityVPSSTP:
[legend]

Detailed Description

MolalityVPSSTP is a derived class of ThermoPhase that handles variable pressure standard state methods for calculating thermodynamic properties that are further based on molality-scaled activities.

This category incorporates most of the methods for calculating liquid electrolyte thermodynamics that have been developed since the 1970's.

This class adds additional functions onto the ThermoPhase interface that handle molality based standard states. The ThermoPhase class includes a member function, ThermoPhase::activityConvention() that indicates which convention the activities are based on. The default is to assume activities are based on the molar convention. However, classes which derive from the MolalityVPSSTP class return cAC_CONVENTION_MOLALITY from this member function.

The molality of a solute, \( m_i \), is defined as

\[ m_i = \frac{n_i}{\tilde{M}_o n_o} \]

where

\[ \tilde{M}_o = \frac{M_o}{1000} \]

where \( M_o \) is the molecular weight of the solvent. The molality has units of gmol/kg. For the solute, the molality may be considered as the amount of gmol's of solute per kg of solvent, a natural experimental quantity.

The formulas for calculating mole fractions if given the molalities of the solutes is stated below. First calculate \( L^{sum} \), an intermediate quantity.

\[ L^{sum} = \frac{1}{\tilde{M}_o X_o} = \frac{1}{\tilde{M}_o} + \sum_{i\ne o} m_i \]

Then,

\[ X_o = \frac{1}{\tilde{M}_o L^{sum}} \]

\[ X_i = \frac{m_i}{L^{sum}} \]

where \( X_o \) is the mole fraction of solvent, and \( X_o \) is the mole fraction of solute i. Thus, the molality scale and the mole fraction scale offer a one-to-one mapping between each other, except in the limit of a zero solvent mole fraction.

The standard states for thermodynamic objects that derive from MolalityVPSSTP are on the unit molality basis. Chemical potentials of the solutes, \( \mu_k \), and the solvent, \( \mu_o \), which are based on the molality form, have the following general format:

\[ \mu_k = \mu^{\triangle}_k(T,P) + R T \ln(\gamma_k^{\triangle} \frac{m_k}{m^\triangle}) \]

\[ \mu_o = \mu^o_o(T,P) + RT \ln(a_o) \]

where \( \gamma_k^{\triangle} \) is the molality based activity coefficient for species \( k \).

The chemical potential of the solvent is thus expressed in a different format than the chemical potential of the solutes. Additionally, the activity of the solvent, \( a_o \), is further reexpressed in terms of an osmotic coefficient, \( \phi \).

\[ \phi = \frac{- \ln(a_o)}{\tilde{M}_o \sum_{i \ne o} m_i} \]

MolalityVPSSTP::osmoticCoefficient() returns the value of \( \phi \). Note there are a few of definitions of the osmotic coefficient floating around. We use the one defined in (Activity Coefficients in Electrolyte Solutions, K. S. Pitzer CRC Press, Boca Raton, 1991, p. 85, Eqn. 28). This definition is most clearly related to theoretical calculation.

The molar-based activity coefficients \( \gamma_k \) may be calculated from the molality-based activity coefficients, \( \gamma_k^\triangle \) by the following formula.

\[ \gamma_k = \frac{\gamma_k^\triangle}{X_o} \]

For purposes of establishing a convention, the molar activity coefficient of the solvent is set equal to the molality-based activity coefficient of the solvent:

\[ \gamma_o = \gamma_o^\triangle \]

The molality-based and molarity-based standard states may be related to one another by the following formula.

\[ \mu_k^\triangle(T,P) = \mu_k^o(T,P) + R T \ln(\tilde{M}_o m^\triangle) \]

An important convention is followed in all routines that derive from MolalityVPSSTP. Standard state thermodynamic functions and reference state thermodynamic functions return the molality-based quantities. Also all functions which return activities return the molality-based activities. The reason for this convention has been discussed in supporting memos. However, it's important because the term in the equation above is non-trivial. For example it's equal to 2.38 kcal/gmol for water at 298 K.

In order to prevent a singularity, this class includes the concept of a minimum value for the solvent mole fraction. All calculations involving the formulation of activity coefficients and other non-ideal solution behavior adhere to this concept of a minimal value for the solvent mole fraction. This makes sense because these solution behavior were all designed and measured far away from the zero solvent singularity condition and are not applicable in that limit.

This objects add a layer that supports molality. It inherits from VPStandardStateTP.

All objects that derive from this are assumed to have molality based standard states.

Molality based activity coefficients are scaled according to the current pH scale. See the Eq3/6 manual for details.

Activity coefficients for species k may be altered between scales s1 to s2 using the following formula

\[ \ln(\gamma_k^{s2}) = \ln(\gamma_k^{s1}) + \frac{z_k}{z_j} \left( \ln(\gamma_j^{s2}) - \ln(\gamma_j^{s1}) \right) \]

where j is any one species. For the NBS scale, j is equal to the Cl- species and

\[ \ln(\gamma_{Cl-}^{s2}) = \frac{-A_{\phi} \sqrt{I}}{1.0 + 1.5 \sqrt{I}} \]

The Pitzer scale doesn't actually change anything. The pitzer scale is defined as the raw unscaled activity coefficients produced by the underlying objects.

SetState Strategy

The MolalityVPSSTP object does not have a setState strategy concerning the molalities. It does not keep track of whether the molalities have changed. It's strictly an interfacial layer that writes the current mole fractions to the State object. When molalities are needed it recalculates the molalities from the State object's mole fraction vector.

Todo:
Make two solvent minimum fractions. One would be for calculation of the non-ideal factors. The other one would be for purposes of stoichiometry evaluation. the stoichiometry evaluation one would be a 1E-13 limit. Anything less would create problems with roundoff error.

Definition at line 226 of file MolalityVPSSTP.h.

Public Member Functions

 MolalityVPSSTP ()
 Default Constructor.
 
void setState_TPM (double t, double p, const double *const molalities)
 Set the temperature (K), pressure (Pa), and molalities (gmol kg-1) of the solutes.
 
void setState_TPM (double t, double p, const Composition &m)
 Set the temperature (K), pressure (Pa), and molalities.
 
void setState_TPM (double t, double p, const string &m)
 Set the temperature (K), pressure (Pa), and molalities.
 
void setState (const AnyMap &state) override
 Set the state using an AnyMap containing any combination of properties supported by the thermodynamic model.
 
void getdlnActCoeffdlnN (const size_t ld, double *const dlnActCoeffdlnN) override
 Get the array of derivatives of the log activity coefficients with respect to the log of the species mole numbers.
 
string report (bool show_thermo=true, double threshold=1e-14) const override
 returns a summary of the state of the phase as a string
 
Utilities
string phaseOfMatter () const override
 String indicating the mechanical phase of the matter in this Phase.
 
void setpHScale (const int pHscaleType)
 Set the pH scale, which determines the scale for single-ion activity coefficients.
 
int pHScale () const
 Reports the pH scale, which determines the scale for single-ion activity coefficients.
 
Utilities for Solvent ID and Molality
void setMoleFSolventMin (double xmolSolventMIN)
 Sets the minimum mole fraction in the molality formulation.
 
double moleFSolventMin () const
 Returns the minimum mole fraction in the molality formulation.
 
void calcMolalities () const
 Calculates the molality of all species and stores the result internally.
 
void getMolalities (double *const molal) const
 This function will return the molalities of the species.
 
void setMolalities (const double *const molal)
 Set the molalities of the solutes in a phase.
 
void setMolalitiesByName (const Composition &xMap)
 Set the molalities of a phase.
 
void setMolalitiesByName (const string &name)
 Set the molalities of a phase.
 
Activities, Standard States, and Activity Concentrations

The activity \( a_k \) of a species in solution is related to the chemical potential by

\[ \mu_k = \mu_k^0(T) + \hat R T \ln a_k. \]

The quantity \( \mu_k^0(T,P) \) is the chemical potential at unit activity, which depends only on temperature and pressure.

int activityConvention () const override
 We set the convention to molality here.
 
void getActivityConcentrations (double *c) const override
 This method returns an array of generalized concentrations.
 
double standardConcentration (size_t k=0) const override
 Return the standard concentration for the kth species.
 
void getActivities (double *ac) const override
 Get the array of non-dimensional activities (molality based for this class and classes that derive from it) at the current solution temperature, pressure, and solution concentration.
 
void getActivityCoefficients (double *ac) const override
 Get the array of non-dimensional activity coefficients at the current solution temperature, pressure, and solution concentration.
 
virtual void getMolalityActivityCoefficients (double *acMolality) const
 Get the array of non-dimensional molality based activity coefficients at the current solution temperature, pressure, and solution concentration.
 
virtual double osmoticCoefficient () const
 Calculate the osmotic coefficient.
 
Initialization

The following methods are used in the process of constructing the phase and setting its parameters from a specification in an input file.

They are not normally used in application programs. To see how they are used, see importPhase().

bool addSpecies (shared_ptr< Species > spec) override
 Add a Species to this Phase.
 
void initThermo () override
 Initialize the ThermoPhase object after all species have been set up.
 
- Public Member Functions inherited from VPStandardStateTP
void setTemperature (const double temp) override
 Set the temperature of the phase.
 
void setPressure (double p) override
 Set the internally stored pressure (Pa) at constant temperature and composition.
 
void setState_TP (double T, double pres) override
 Set the temperature and pressure at the same time.
 
double pressure () const override
 Returns the current pressure of the phase.
 
virtual void updateStandardStateThermo () const
 Updates the standard state thermodynamic functions at the current T and P of the solution.
 
double minTemp (size_t k=npos) const override
 Minimum temperature for which the thermodynamic data for the species or phase are valid.
 
double maxTemp (size_t k=npos) const override
 Maximum temperature for which the thermodynamic data for the species are valid.
 
PDSSprovidePDSS (size_t k)
 
const PDSSprovidePDSS (size_t k) const
 
 VPStandardStateTP ()
 Constructor.
 
bool isCompressible () const override
 Return whether phase represents a compressible substance.
 
int standardStateConvention () const override
 This method returns the convention used in specification of the standard state, of which there are currently two, temperature based, and variable pressure based.
 
void getStandardChemPotentials (double *mu) const override
 Get the array of chemical potentials at unit activity for the species at their standard states at the current T and P of the solution.
 
void getEnthalpy_RT (double *hrt) const override
 Get the nondimensional Enthalpy functions for the species at their standard states at the current T and P of the solution.
 
void getEntropy_R (double *sr) const override
 Get the array of nondimensional Entropy functions for the standard state species at the current T and P of the solution.
 
void getGibbs_RT (double *grt) const override
 Get the nondimensional Gibbs functions for the species in their standard states at the current T and P of the solution.
 
void getPureGibbs (double *gpure) const override
 Get the Gibbs functions for the standard state of the species at the current T and P of the solution.
 
void getIntEnergy_RT (double *urt) const override
 Returns the vector of nondimensional Internal Energies of the standard state species at the current T and P of the solution.
 
void getCp_R (double *cpr) const override
 Get the nondimensional Heat Capacities at constant pressure for the species standard states at the current T and P of the solution.
 
void getStandardVolumes (double *vol) const override
 Get the molar volumes of the species standard states at the current T and P of the solution.
 
virtual const vector< double > & getStandardVolumes () const
 
void initThermo () override
 Initialize the ThermoPhase object after all species have been set up.
 
void getSpeciesParameters (const string &name, AnyMap &speciesNode) const override
 Get phase-specific parameters of a Species object such that an identical one could be reconstructed and added to this phase.
 
bool addSpecies (shared_ptr< Species > spec) override
 Add a Species to this Phase.
 
void installPDSS (size_t k, unique_ptr< PDSS > &&pdss)
 Install a PDSS object for species k
 
virtual bool addSpecies (shared_ptr< Species > spec)
 Add a Species to this Phase.
 
void getEnthalpy_RT_ref (double *hrt) const override
 Returns the vector of nondimensional enthalpies of the reference state at the current temperature of the solution and the reference pressure for the species.
 
void getGibbs_RT_ref (double *grt) const override
 Returns the vector of nondimensional Gibbs Free Energies of the reference state at the current temperature of the solution and the reference pressure for the species.
 
void getGibbs_ref (double *g) const override
 Returns the vector of the Gibbs function of the reference state at the current temperature of the solution and the reference pressure for the species.
 
void getEntropy_R_ref (double *er) const override
 Returns the vector of nondimensional entropies of the reference state at the current temperature of the solution and the reference pressure for each species.
 
void getCp_R_ref (double *cprt) const override
 Returns the vector of nondimensional constant pressure heat capacities of the reference state at the current temperature of the solution and reference pressure for each species.
 
void getStandardVolumes_ref (double *vol) const override
 Get the molar volumes of the species reference states at the current T and P_ref of the solution.
 
- Public Member Functions inherited from ThermoPhase
 ThermoPhase ()=default
 Constructor.
 
double RT () const
 Return the Gas Constant multiplied by the current temperature.
 
double equivalenceRatio () const
 Compute the equivalence ratio for the current mixture from available oxygen and required oxygen.
 
string type () const override
 String indicating the thermodynamic model implemented.
 
virtual bool isIdeal () const
 Boolean indicating whether phase is ideal.
 
virtual double refPressure () const
 Returns the reference pressure in Pa.
 
double Hf298SS (const size_t k) const
 Report the 298 K Heat of Formation of the standard state of one species (J kmol-1)
 
virtual void modifyOneHf298SS (const size_t k, const double Hf298New)
 Modify the value of the 298 K Heat of Formation of one species in the phase (J kmol-1)
 
virtual void resetHf298 (const size_t k=npos)
 Restore the original heat of formation of one or more species.
 
bool chargeNeutralityNecessary () const
 Returns the chargeNeutralityNecessity boolean.
 
virtual double enthalpy_mole () const
 Molar enthalpy. Units: J/kmol.
 
virtual double intEnergy_mole () const
 Molar internal energy. Units: J/kmol.
 
virtual double entropy_mole () const
 Molar entropy. Units: J/kmol/K.
 
virtual double gibbs_mole () const
 Molar Gibbs function. Units: J/kmol.
 
virtual double cp_mole () const
 Molar heat capacity at constant pressure. Units: J/kmol/K.
 
virtual double cv_mole () const
 Molar heat capacity at constant volume. Units: J/kmol/K.
 
virtual double isothermalCompressibility () const
 Returns the isothermal compressibility. Units: 1/Pa.
 
virtual double thermalExpansionCoeff () const
 Return the volumetric thermal expansion coefficient. Units: 1/K.
 
virtual double soundSpeed () const
 Return the speed of sound. Units: m/s.
 
void setElectricPotential (double v)
 Set the electric potential of this phase (V).
 
double electricPotential () const
 Returns the electric potential of this phase (V).
 
virtual Units standardConcentrationUnits () const
 Returns the units of the "standard concentration" for this phase.
 
virtual double logStandardConc (size_t k=0) const
 Natural logarithm of the standard concentration of the kth species.
 
virtual void getLnActivityCoefficients (double *lnac) const
 Get the array of non-dimensional molar-based ln activity coefficients at the current solution temperature, pressure, and solution concentration.
 
virtual void getChemPotentials (double *mu) const
 Get the species chemical potentials. Units: J/kmol.
 
void getElectrochemPotentials (double *mu) const
 Get the species electrochemical potentials.
 
virtual void getPartialMolarEnthalpies (double *hbar) const
 Returns an array of partial molar enthalpies for the species in the mixture.
 
virtual void getPartialMolarEntropies (double *sbar) const
 Returns an array of partial molar entropies of the species in the solution.
 
virtual void getPartialMolarIntEnergies (double *ubar) const
 Return an array of partial molar internal energies for the species in the mixture.
 
virtual void getPartialMolarCp (double *cpbar) const
 Return an array of partial molar heat capacities for the species in the mixture.
 
virtual void getPartialMolarVolumes (double *vbar) const
 Return an array of partial molar volumes for the species in the mixture.
 
virtual void getIntEnergy_RT_ref (double *urt) const
 Returns the vector of nondimensional internal Energies of the reference state at the current temperature of the solution and the reference pressure for each species.
 
double enthalpy_mass () const
 Specific enthalpy. Units: J/kg.
 
double intEnergy_mass () const
 Specific internal energy. Units: J/kg.
 
double entropy_mass () const
 Specific entropy. Units: J/kg/K.
 
double gibbs_mass () const
 Specific Gibbs function. Units: J/kg.
 
double cp_mass () const
 Specific heat at constant pressure. Units: J/kg/K.
 
double cv_mass () const
 Specific heat at constant volume. Units: J/kg/K.
 
virtual void setState_TPX (double t, double p, const double *x)
 Set the temperature (K), pressure (Pa), and mole fractions.
 
virtual void setState_TPX (double t, double p, const Composition &x)
 Set the temperature (K), pressure (Pa), and mole fractions.
 
virtual void setState_TPX (double t, double p, const string &x)
 Set the temperature (K), pressure (Pa), and mole fractions.
 
virtual void setState_TPY (double t, double p, const double *y)
 Set the internally stored temperature (K), pressure (Pa), and mass fractions of the phase.
 
virtual void setState_TPY (double t, double p, const Composition &y)
 Set the internally stored temperature (K), pressure (Pa), and mass fractions of the phase.
 
virtual void setState_TPY (double t, double p, const string &y)
 Set the internally stored temperature (K), pressure (Pa), and mass fractions of the phase.
 
virtual void setState_HP (double h, double p, double tol=1e-9)
 Set the internally stored specific enthalpy (J/kg) and pressure (Pa) of the phase.
 
virtual void setState_UV (double u, double v, double tol=1e-9)
 Set the specific internal energy (J/kg) and specific volume (m^3/kg).
 
virtual void setState_SP (double s, double p, double tol=1e-9)
 Set the specific entropy (J/kg/K) and pressure (Pa).
 
virtual void setState_SV (double s, double v, double tol=1e-9)
 Set the specific entropy (J/kg/K) and specific volume (m^3/kg).
 
virtual void setState_ST (double s, double t, double tol=1e-9)
 Set the specific entropy (J/kg/K) and temperature (K).
 
virtual void setState_TV (double t, double v, double tol=1e-9)
 Set the temperature (K) and specific volume (m^3/kg).
 
virtual void setState_PV (double p, double v, double tol=1e-9)
 Set the pressure (Pa) and specific volume (m^3/kg).
 
virtual void setState_UP (double u, double p, double tol=1e-9)
 Set the specific internal energy (J/kg) and pressure (Pa).
 
virtual void setState_VH (double v, double h, double tol=1e-9)
 Set the specific volume (m^3/kg) and the specific enthalpy (J/kg)
 
virtual void setState_TH (double t, double h, double tol=1e-9)
 Set the temperature (K) and the specific enthalpy (J/kg)
 
virtual void setState_SH (double s, double h, double tol=1e-9)
 Set the specific entropy (J/kg/K) and the specific enthalpy (J/kg)
 
virtual void setState_DP (double rho, double p)
 Set the density (kg/m**3) and pressure (Pa) at constant composition.
 
void setMixtureFraction (double mixFrac, const double *fuelComp, const double *oxComp, ThermoBasis basis=ThermoBasis::molar)
 Set the mixture composition according to the mixture fraction = kg fuel / (kg oxidizer + kg fuel)
 
void setMixtureFraction (double mixFrac, const string &fuelComp, const string &oxComp, ThermoBasis basis=ThermoBasis::molar)
 Set the mixture composition according to the mixture fraction = kg fuel / (kg oxidizer + kg fuel)
 
void setMixtureFraction (double mixFrac, const Composition &fuelComp, const Composition &oxComp, ThermoBasis basis=ThermoBasis::molar)
 Set the mixture composition according to the mixture fraction = kg fuel / (kg oxidizer + kg fuel)
 
double mixtureFraction (const double *fuelComp, const double *oxComp, ThermoBasis basis=ThermoBasis::molar, const string &element="Bilger") const
 Compute the mixture fraction = kg fuel / (kg oxidizer + kg fuel) for the current mixture given fuel and oxidizer compositions.
 
double mixtureFraction (const string &fuelComp, const string &oxComp, ThermoBasis basis=ThermoBasis::molar, const string &element="Bilger") const
 Compute the mixture fraction = kg fuel / (kg oxidizer + kg fuel) for the current mixture given fuel and oxidizer compositions.
 
double mixtureFraction (const Composition &fuelComp, const Composition &oxComp, ThermoBasis basis=ThermoBasis::molar, const string &element="Bilger") const
 Compute the mixture fraction = kg fuel / (kg oxidizer + kg fuel) for the current mixture given fuel and oxidizer compositions.
 
void setEquivalenceRatio (double phi, const double *fuelComp, const double *oxComp, ThermoBasis basis=ThermoBasis::molar)
 Set the mixture composition according to the equivalence ratio.
 
void setEquivalenceRatio (double phi, const string &fuelComp, const string &oxComp, ThermoBasis basis=ThermoBasis::molar)
 Set the mixture composition according to the equivalence ratio.
 
void setEquivalenceRatio (double phi, const Composition &fuelComp, const Composition &oxComp, ThermoBasis basis=ThermoBasis::molar)
 Set the mixture composition according to the equivalence ratio.
 
double equivalenceRatio (const double *fuelComp, const double *oxComp, ThermoBasis basis=ThermoBasis::molar) const
 Compute the equivalence ratio for the current mixture given the compositions of fuel and oxidizer.
 
double equivalenceRatio (const string &fuelComp, const string &oxComp, ThermoBasis basis=ThermoBasis::molar) const
 Compute the equivalence ratio for the current mixture given the compositions of fuel and oxidizer.
 
double equivalenceRatio (const Composition &fuelComp, const Composition &oxComp, ThermoBasis basis=ThermoBasis::molar) const
 Compute the equivalence ratio for the current mixture given the compositions of fuel and oxidizer.
 
double stoichAirFuelRatio (const double *fuelComp, const double *oxComp, ThermoBasis basis=ThermoBasis::molar) const
 Compute the stoichiometric air to fuel ratio (kg oxidizer / kg fuel) given fuel and oxidizer compositions.
 
double stoichAirFuelRatio (const string &fuelComp, const string &oxComp, ThermoBasis basis=ThermoBasis::molar) const
 Compute the stoichiometric air to fuel ratio (kg oxidizer / kg fuel) given fuel and oxidizer compositions.
 
double stoichAirFuelRatio (const Composition &fuelComp, const Composition &oxComp, ThermoBasis basis=ThermoBasis::molar) const
 Compute the stoichiometric air to fuel ratio (kg oxidizer / kg fuel) given fuel and oxidizer compositions.
 
void equilibrate (const string &XY, const string &solver="auto", double rtol=1e-9, int max_steps=50000, int max_iter=100, int estimate_equil=0, int log_level=0)
 Equilibrate a ThermoPhase object.
 
virtual void setToEquilState (const double *mu_RT)
 This method is used by the ChemEquil equilibrium solver.
 
virtual bool compatibleWithMultiPhase () const
 Indicates whether this phase type can be used with class MultiPhase for equilibrium calculations.
 
virtual double critTemperature () const
 Critical temperature (K).
 
virtual double critPressure () const
 Critical pressure (Pa).
 
virtual double critVolume () const
 Critical volume (m3/kmol).
 
virtual double critCompressibility () const
 Critical compressibility (unitless).
 
virtual double critDensity () const
 Critical density (kg/m3).
 
virtual double satTemperature (double p) const
 Return the saturation temperature given the pressure.
 
virtual double satPressure (double t)
 Return the saturation pressure given the temperature.
 
virtual double vaporFraction () const
 Return the fraction of vapor at the current conditions.
 
virtual void setState_Tsat (double t, double x)
 Set the state to a saturated system at a particular temperature.
 
virtual void setState_Psat (double p, double x)
 Set the state to a saturated system at a particular pressure.
 
void setState_TPQ (double T, double P, double Q)
 Set the temperature, pressure, and vapor fraction (quality).
 
void modifySpecies (size_t k, shared_ptr< Species > spec) override
 Modify the thermodynamic data associated with a species.
 
virtual MultiSpeciesThermospeciesThermo (int k=-1)
 Return a changeable reference to the calculation manager for species reference-state thermodynamic properties.
 
virtual const MultiSpeciesThermospeciesThermo (int k=-1) const
 
void initThermoFile (const string &inputFile, const string &id)
 Initialize a ThermoPhase object using an input file.
 
virtual void setParameters (const AnyMap &phaseNode, const AnyMap &rootNode=AnyMap())
 Set equation of state parameters from an AnyMap phase description.
 
AnyMap parameters (bool withInput=true) const
 Returns the parameters of a ThermoPhase object such that an identical one could be reconstructed using the newThermo(AnyMap&) function.
 
const AnyMapinput () const
 Access input data associated with the phase description.
 
AnyMapinput ()
 
virtual void getdlnActCoeffds (const double dTds, const double *const dXds, double *dlnActCoeffds) const
 Get the change in activity coefficients wrt changes in state (temp, mole fraction, etc) along a line in parameter space or along a line in physical space.
 
virtual void getdlnActCoeffdlnX_diag (double *dlnActCoeffdlnX_diag) const
 Get the array of ln mole fraction derivatives of the log activity coefficients - diagonal component only.
 
virtual void getdlnActCoeffdlnN_diag (double *dlnActCoeffdlnN_diag) const
 Get the array of log species mole number derivatives of the log activity coefficients.
 
virtual void getdlnActCoeffdlnN_numderiv (const size_t ld, double *const dlnActCoeffdlnN)
 
- Public Member Functions inherited from Phase
 Phase ()=default
 Default constructor.
 
 Phase (const Phase &)=delete
 
Phaseoperator= (const Phase &)=delete
 
virtual bool isPure () const
 Return whether phase represents a pure (single species) substance.
 
virtual bool hasPhaseTransition () const
 Return whether phase represents a substance with phase transitions.
 
virtual bool isCompressible () const
 Return whether phase represents a compressible substance.
 
virtual map< string, size_t > nativeState () const
 Return a map of properties defining the native state of a substance.
 
string nativeMode () const
 Return string acronym representing the native state of a Phase.
 
virtual vector< string > fullStates () const
 Return a vector containing full states defining a phase.
 
virtual vector< string > partialStates () const
 Return a vector of settable partial property sets within a phase.
 
virtual size_t stateSize () const
 Return size of vector defining internal state of the phase.
 
void saveState (vector< double > &state) const
 Save the current internal state of the phase.
 
virtual void saveState (size_t lenstate, double *state) const
 Write to array 'state' the current internal state.
 
void restoreState (const vector< double > &state)
 Restore a state saved on a previous call to saveState.
 
virtual void restoreState (size_t lenstate, const double *state)
 Restore the state of the phase from a previously saved state vector.
 
double molecularWeight (size_t k) const
 Molecular weight of species k.
 
void getMolecularWeights (double *weights) const
 Copy the vector of molecular weights into array weights.
 
const vector< double > & molecularWeights () const
 Return a const reference to the internal vector of molecular weights.
 
const vector< double > & inverseMolecularWeights () const
 Return a const reference to the internal vector of molecular weights.
 
void getCharges (double *charges) const
 Copy the vector of species charges into array charges.
 
virtual void setMolesNoTruncate (const double *const N)
 Set the state of the object with moles in [kmol].
 
double elementalMassFraction (const size_t m) const
 Elemental mass fraction of element m.
 
double elementalMoleFraction (const size_t m) const
 Elemental mole fraction of element m.
 
double charge (size_t k) const
 Dimensionless electrical charge of a single molecule of species k The charge is normalized by the the magnitude of the electron charge.
 
double chargeDensity () const
 Charge density [C/m^3].
 
size_t nDim () const
 Returns the number of spatial dimensions (1, 2, or 3)
 
void setNDim (size_t ndim)
 Set the number of spatial dimensions (1, 2, or 3).
 
virtual bool ready () const
 Returns a bool indicating whether the object is ready for use.
 
int stateMFNumber () const
 Return the State Mole Fraction Number.
 
virtual void invalidateCache ()
 Invalidate any cached values which are normally updated only when a change in state is detected.
 
bool caseSensitiveSpecies () const
 Returns true if case sensitive species names are enforced.
 
void setCaseSensitiveSpecies (bool cflag=true)
 Set flag that determines whether case sensitive species are enforced in look-up operations, for example speciesIndex.
 
vector< double > getCompositionFromMap (const Composition &comp) const
 Converts a Composition to a vector with entries for each species Species that are not specified are set to zero in the vector.
 
void massFractionsToMoleFractions (const double *Y, double *X) const
 Converts a mixture composition from mole fractions to mass fractions.
 
void moleFractionsToMassFractions (const double *X, double *Y) const
 Converts a mixture composition from mass fractions to mole fractions.
 
string name () const
 Return the name of the phase.
 
void setName (const string &nm)
 Sets the string name for the phase.
 
string elementName (size_t m) const
 Name of the element with index m.
 
size_t elementIndex (const string &name) const
 Return the index of element named 'name'.
 
const vector< string > & elementNames () const
 Return a read-only reference to the vector of element names.
 
double atomicWeight (size_t m) const
 Atomic weight of element m.
 
double entropyElement298 (size_t m) const
 Entropy of the element in its standard state at 298 K and 1 bar.
 
int atomicNumber (size_t m) const
 Atomic number of element m.
 
int elementType (size_t m) const
 Return the element constraint type Possible types include:
 
int changeElementType (int m, int elem_type)
 Change the element type of the mth constraint Reassigns an element type.
 
const vector< double > & atomicWeights () const
 Return a read-only reference to the vector of atomic weights.
 
size_t nElements () const
 Number of elements.
 
void checkElementIndex (size_t m) const
 Check that the specified element index is in range.
 
void checkElementArraySize (size_t mm) const
 Check that an array size is at least nElements().
 
double nAtoms (size_t k, size_t m) const
 Number of atoms of element m in species k.
 
size_t speciesIndex (const string &name) const
 Returns the index of a species named 'name' within the Phase object.
 
string speciesName (size_t k) const
 Name of the species with index k.
 
const vector< string > & speciesNames () const
 Return a const reference to the vector of species names.
 
size_t nSpecies () const
 Returns the number of species in the phase.
 
void checkSpeciesIndex (size_t k) const
 Check that the specified species index is in range.
 
void checkSpeciesArraySize (size_t kk) const
 Check that an array size is at least nSpecies().
 
void setMoleFractionsByName (const Composition &xMap)
 Set the species mole fractions by name.
 
void setMoleFractionsByName (const string &x)
 Set the mole fractions of a group of species by name.
 
void setMassFractionsByName (const Composition &yMap)
 Set the species mass fractions by name.
 
void setMassFractionsByName (const string &x)
 Set the species mass fractions by name.
 
void setState_TD (double t, double rho)
 Set the internally stored temperature (K) and density (kg/m^3)
 
Composition getMoleFractionsByName (double threshold=0.0) const
 Get the mole fractions by name.
 
double moleFraction (size_t k) const
 Return the mole fraction of a single species.
 
double moleFraction (const string &name) const
 Return the mole fraction of a single species.
 
Composition getMassFractionsByName (double threshold=0.0) const
 Get the mass fractions by name.
 
double massFraction (size_t k) const
 Return the mass fraction of a single species.
 
double massFraction (const string &name) const
 Return the mass fraction of a single species.
 
void getMoleFractions (double *const x) const
 Get the species mole fraction vector.
 
virtual void setMoleFractions (const double *const x)
 Set the mole fractions to the specified values.
 
virtual void setMoleFractions_NoNorm (const double *const x)
 Set the mole fractions to the specified values without normalizing.
 
void getMassFractions (double *const y) const
 Get the species mass fractions.
 
const double * massFractions () const
 Return a const pointer to the mass fraction array.
 
virtual void setMassFractions (const double *const y)
 Set the mass fractions to the specified values and normalize them.
 
virtual void setMassFractions_NoNorm (const double *const y)
 Set the mass fractions to the specified values without normalizing.
 
virtual void getConcentrations (double *const c) const
 Get the species concentrations (kmol/m^3).
 
virtual double concentration (const size_t k) const
 Concentration of species k.
 
virtual void setConcentrations (const double *const conc)
 Set the concentrations to the specified values within the phase.
 
virtual void setConcentrationsNoNorm (const double *const conc)
 Set the concentrations without ignoring negative concentrations.
 
double temperature () const
 Temperature (K).
 
virtual double electronTemperature () const
 Electron Temperature (K)
 
virtual double density () const
 Density (kg/m^3).
 
virtual double molarDensity () const
 Molar density (kmol/m^3).
 
virtual double molarVolume () const
 Molar volume (m^3/kmol).
 
virtual void setDensity (const double density_)
 Set the internally stored density (kg/m^3) of the phase.
 
virtual void setElectronTemperature (double etemp)
 Set the internally stored electron temperature of the phase (K).
 
double mean_X (const double *const Q) const
 Evaluate the mole-fraction-weighted mean of an array Q.
 
double mean_X (const vector< double > &Q) const
 Evaluate the mole-fraction-weighted mean of an array Q.
 
double meanMolecularWeight () const
 The mean molecular weight. Units: (kg/kmol)
 
double sum_xlogx () const
 Evaluate \( \sum_k X_k \ln X_k \).
 
size_t addElement (const string &symbol, double weight=-12345.0, int atomicNumber=0, double entropy298=ENTROPY298_UNKNOWN, int elem_type=CT_ELEM_TYPE_ABSPOS)
 Add an element.
 
void addSpeciesAlias (const string &name, const string &alias)
 Add a species alias (that is, a user-defined alternative species name).
 
virtual vector< string > findIsomers (const Composition &compMap) const
 Return a vector with isomers names matching a given composition map.
 
virtual vector< string > findIsomers (const string &comp) const
 Return a vector with isomers names matching a given composition string.
 
shared_ptr< Speciesspecies (const string &name) const
 Return the Species object for the named species.
 
shared_ptr< Speciesspecies (size_t k) const
 Return the Species object for species whose index is k.
 
void ignoreUndefinedElements ()
 Set behavior when adding a species containing undefined elements to just skip the species.
 
void addUndefinedElements ()
 Set behavior when adding a species containing undefined elements to add those elements to the phase.
 
void throwUndefinedElements ()
 Set the behavior when adding a species containing undefined elements to throw an exception.
 

Protected Member Functions

virtual void getUnscaledMolalityActivityCoefficients (double *acMolality) const
 Get the array of unscaled non-dimensional molality based activity coefficients at the current solution temperature, pressure, and solution concentration.
 
virtual void applyphScale (double *acMolality) const
 Apply the current phScale to a set of activity Coefficients or activities.
 
- Protected Member Functions inherited from VPStandardStateTP
virtual void calcDensity ()
 Calculate the density of the mixture using the partial molar volumes and mole fractions as input.
 
virtual void _updateStandardStateThermo () const
 Updates the standard state thermodynamic functions at the current T and P of the solution.
 
void invalidateCache () override
 Invalidate any cached values which are normally updated only when a change in state is detected.
 
const vector< double > & Gibbs_RT_ref () const
 
- Protected Member Functions inherited from ThermoPhase
virtual void getParameters (AnyMap &phaseNode) const
 Store the parameters of a ThermoPhase object such that an identical one could be reconstructed using the newThermo(AnyMap&) function.
 
- Protected Member Functions inherited from Phase
void assertCompressible (const string &setter) const
 Ensure that phase is compressible.
 
void assignDensity (const double density_)
 Set the internally stored constant density (kg/m^3) of the phase.
 
void setMolecularWeight (const int k, const double mw)
 Set the molecular weight of a single species to a given value.
 
virtual void compositionChanged ()
 Apply changes to the state which are needed after the composition changes.
 

Protected Attributes

int m_pHScalingType = PHSCALE_PITZER
 Scaling to be used for output of single-ion species activity coefficients.
 
size_t m_indexCLM = npos
 Index of the phScale species.
 
double m_weightSolvent = 18.01528
 Molecular weight of the Solvent.
 
double m_xmolSolventMIN = 0.01
 In any molality implementation, it makes sense to have a minimum solvent mole fraction requirement, since the implementation becomes singular in the xmolSolvent=0 limit.
 
double m_Mnaught = 18.01528E-3
 This is the multiplication factor that goes inside log expressions involving the molalities of species.
 
vector< double > m_molalities
 Current value of the molalities of the species in the phase.
 
- Protected Attributes inherited from VPStandardStateTP
double m_Pcurrent = OneAtm
 Current value of the pressure - state variable.
 
double m_minTemp = 0.0
 The minimum temperature at which data for all species is valid.
 
double m_maxTemp = BigNumber
 The maximum temperature at which data for all species is valid.
 
double m_Tlast_ss = -1.0
 The last temperature at which the standard state thermodynamic properties were calculated at.
 
double m_Plast_ss = -1.0
 The last pressure at which the Standard State thermodynamic properties were calculated at.
 
vector< unique_ptr< PDSS > > m_PDSS_storage
 Storage for the PDSS objects for the species.
 
vector< double > m_h0_RT
 Vector containing the species reference enthalpies at T = m_tlast and P = p_ref.
 
vector< double > m_cp0_R
 Vector containing the species reference constant pressure heat capacities at T = m_tlast and P = p_ref.
 
vector< double > m_g0_RT
 Vector containing the species reference Gibbs functions at T = m_tlast and P = p_ref.
 
vector< double > m_s0_R
 Vector containing the species reference entropies at T = m_tlast and P = p_ref.
 
vector< double > m_V0
 Vector containing the species reference molar volumes.
 
vector< double > m_hss_RT
 Vector containing the species Standard State enthalpies at T = m_tlast and P = m_plast.
 
vector< double > m_cpss_R
 Vector containing the species Standard State constant pressure heat capacities at T = m_tlast and P = m_plast.
 
vector< double > m_gss_RT
 Vector containing the species Standard State Gibbs functions at T = m_tlast and P = m_plast.
 
vector< double > m_sss_R
 Vector containing the species Standard State entropies at T = m_tlast and P = m_plast.
 
vector< double > m_Vss
 Vector containing the species standard state volumes at T = m_tlast and P = m_plast.
 
- Protected Attributes inherited from ThermoPhase
MultiSpeciesThermo m_spthermo
 Pointer to the calculation manager for species reference-state thermodynamic properties.
 
AnyMap m_input
 Data supplied via setParameters.
 
double m_phi = 0.0
 Stored value of the electric potential for this phase. Units are Volts.
 
bool m_chargeNeutralityNecessary = false
 Boolean indicating whether a charge neutrality condition is a necessity.
 
int m_ssConvention = cSS_CONVENTION_TEMPERATURE
 Contains the standard state convention.
 
double m_tlast = 0.0
 last value of the temperature processed by reference state
 
- Protected Attributes inherited from Phase
ValueCache m_cache
 Cached for saved calculations within each ThermoPhase.
 
size_t m_kk = 0
 Number of species in the phase.
 
size_t m_ndim = 3
 Dimensionality of the phase.
 
vector< double > m_speciesComp
 Atomic composition of the species.
 
vector< double > m_speciesCharge
 Vector of species charges. length m_kk.
 
map< string, shared_ptr< Species > > m_species
 
UndefElement::behavior m_undefinedElementBehavior = UndefElement::add
 Flag determining behavior when adding species with an undefined element.
 
bool m_caseSensitiveSpecies = false
 Flag determining whether case sensitive species names are enforced.
 

Private Member Functions

size_t findCLMIndex () const
 Returns the index of the Cl- species.
 

Constructor & Destructor Documentation

◆ MolalityVPSSTP()

Default Constructor.

This doesn't do much more than initialize constants with default values for water at 25C. Water molecular weight comes from the default elements definitions. It actually differs slightly from the IAPWS95 value of 18.015268. However, density conservation and therefore element conservation is the more important principle to follow.

Definition at line 21 of file MolalityVPSSTP.cpp.

Member Function Documentation

◆ phaseOfMatter()

string phaseOfMatter ( ) const
inlineoverridevirtual

String indicating the mechanical phase of the matter in this Phase.

All derived phases from MolalityVPSSTP always represent liquids.

Reimplemented from ThermoPhase.

Definition at line 246 of file MolalityVPSSTP.h.

◆ setpHScale()

void setpHScale ( const int  pHscaleType)

Set the pH scale, which determines the scale for single-ion activity coefficients.

Single ion activity coefficients are not unique in terms of the representing actual measurable quantities.

Parameters
pHscaleTypeInteger representing the pHscale

Definition at line 31 of file MolalityVPSSTP.cpp.

◆ pHScale()

int pHScale ( ) const

Reports the pH scale, which determines the scale for single-ion activity coefficients.

Single ion activity coefficients are not unique in terms of the representing actual measurable quantities.

Returns
the pHscale type

Definition at line 40 of file MolalityVPSSTP.cpp.

◆ setMoleFSolventMin()

void setMoleFSolventMin ( double  xmolSolventMIN)

Sets the minimum mole fraction in the molality formulation.

Note the molality formulation is singular in the limit that the solvent mole fraction goes to zero. Numerically, how this limit is treated and resolved is an ongoing issue within Cantera. The minimum mole fraction must be in the range 0 to 0.9.

Parameters
xmolSolventMINInput double containing the minimum mole fraction

Definition at line 45 of file MolalityVPSSTP.cpp.

◆ moleFSolventMin()

double moleFSolventMin ( ) const

Returns the minimum mole fraction in the molality formulation.

Definition at line 55 of file MolalityVPSSTP.cpp.

◆ calcMolalities()

void calcMolalities ( ) const

Calculates the molality of all species and stores the result internally.

We calculate the vector of molalities of the species in the phase and store the result internally:

\[ m_i = \frac{X_i}{1000 * M_o * X_{o,p}} \]

where

  • \( M_o \) is the molecular weight of the solvent
  • \( X_o \) is the mole fraction of the solvent
  • \( X_i \) is the mole fraction of the solute.
  • \( X_{o,p} = \max (X_{o}^{min}, X_o) \)
  • \( X_{o}^{min} \) = minimum mole fraction of solvent allowed in the denominator.

Definition at line 60 of file MolalityVPSSTP.cpp.

◆ getMolalities()

void getMolalities ( double *const  molal) const

This function will return the molalities of the species.

We calculate the vector of molalities of the species in the phase

\[ m_i = \frac{X_i}{1000 * M_o * X_{o,p}} \]

where

  • \( M_o \) is the molecular weight of the solvent
  • \( X_o \) is the mole fraction of the solvent
  • \( X_i \) is the mole fraction of the solute.
  • \( X_{o,p} = \max (X_{o}^{min}, X_o) \)
  • \( X_{o}^{min} \) = minimum mole fraction of solvent allowed in the denominator.
Parameters
molalOutput vector of molalities. Length: m_kk.

Definition at line 70 of file MolalityVPSSTP.cpp.

◆ setMolalities()

void setMolalities ( const double *const  molal)

Set the molalities of the solutes in a phase.

Note, the entry for the solvent is not used. We are supplied with the molalities of all of the solute species. We then calculate the mole fractions of all species and update the ThermoPhase object.

\[ m_i = \frac{X_i}{M_o/1000 * X_{o,p}} \]

where

  • \( M_o \) is the molecular weight of the solvent
  • \( X_o \) is the mole fraction of the solvent
  • \( X_i \) is the mole fraction of the solute.
  • \( X_{o,p} = \max(X_o^{min}, X_o) \)
  • \( X_o^{min} \) = minimum mole fraction of solvent allowed in the denominator.

The formulas for calculating mole fractions are

\[ L^{sum} = \frac{1}{\tilde{M}_o X_o} = \frac{1}{\tilde{M}_o} + \sum_{i\ne o} m_i \]

Then,

\[ X_o = \frac{1}{\tilde{M}_o L^{sum}} \]

\[ X_i = \frac{m_i}{L^{sum}} \]

It is currently an error if the solvent mole fraction is attempted to be set to a value lower than \( X_o^{min} \).

Parameters
molalInput vector of molalities. Length: m_kk.

Definition at line 78 of file MolalityVPSSTP.cpp.

◆ setMolalitiesByName() [1/2]

void setMolalitiesByName ( const Composition xMap)

Set the molalities of a phase.

Set the molalities of the solutes in a phase. Note, the entry for the solvent is not used.

Parameters
xMapComposition Map containing the molalities.

Definition at line 105 of file MolalityVPSSTP.cpp.

◆ setMolalitiesByName() [2/2]

void setMolalitiesByName ( const string &  name)

Set the molalities of a phase.

Set the molalities of the solutes in a phase. Note, the entry for the solvent is not used.

Parameters
nameString containing the information for a composition map.

Definition at line 173 of file MolalityVPSSTP.cpp.

◆ activityConvention()

int activityConvention ( ) const
overridevirtual

We set the convention to molality here.

Reimplemented from ThermoPhase.

Definition at line 181 of file MolalityVPSSTP.cpp.

◆ getActivityConcentrations()

void getActivityConcentrations ( double *  c) const
overridevirtual

This method returns an array of generalized concentrations.

\( C^a_k \) are defined such that \( a_k = C^a_k / C^0_k, \) where \( C^0_k \) is a standard concentration defined below and \( a_k \) are activities used in the thermodynamic functions. These activity (or generalized) concentrations are used by kinetics manager classes to compute the forward and reverse rates of elementary reactions. Note that they may or may not have units of concentration — they might be partial pressures, mole fractions, or surface coverages, for example.

Parameters
cOutput array of generalized concentrations. The units depend upon the implementation of the reaction rate expressions within the phase.

Reimplemented from ThermoPhase.

Definition at line 186 of file MolalityVPSSTP.cpp.

◆ standardConcentration()

double standardConcentration ( size_t  k = 0) const
overridevirtual

Return the standard concentration for the kth species.

The standard concentration \( C^0_k \) used to normalize the activity (that is, generalized) concentration. In many cases, this quantity will be the same for all species in a phase - for example, for an ideal gas \( C^0_k = P/\hat R T \). For this reason, this method returns a single value, instead of an array. However, for phases in which the standard concentration is species-specific (such as surface species of different sizes), this method may be called with an optional parameter indicating the species.

Parameters
kOptional parameter indicating the species. The default is to assume this refers to species 0.
Returns
Returns the standard concentration. The units are by definition dependent on the ThermoPhase and kinetics manager representation.

Reimplemented from ThermoPhase.

Definition at line 191 of file MolalityVPSSTP.cpp.

◆ getActivities()

void getActivities ( double *  ac) const
overridevirtual

Get the array of non-dimensional activities (molality based for this class and classes that derive from it) at the current solution temperature, pressure, and solution concentration.

All standard state properties for molality-based phases are evaluated consistent with the molality scale. Therefore, this function must return molality-based activities.

\[ a_i^\triangle = \gamma_k^{\triangle} \frac{m_k}{m^\triangle} \]

This function must be implemented in derived classes.

Parameters
acOutput vector of molality-based activities. Length: m_kk.

Reimplemented from ThermoPhase.

Definition at line 196 of file MolalityVPSSTP.cpp.

◆ getActivityCoefficients()

void getActivityCoefficients ( double *  ac) const
overridevirtual

Get the array of non-dimensional activity coefficients at the current solution temperature, pressure, and solution concentration.

These are mole-fraction based activity coefficients. In this object, their calculation is based on translating the values of the molality-based activity coefficients. See Denbigh p. 278 [5] for a thorough discussion.

The molar-based activity coefficients \( \gamma_k \) may be calculated from the molality-based activity coefficients, \( \gamma_k^\triangle \) by the following formula.

\[ \gamma_k = \frac{\gamma_k^\triangle}{X_o} \]

For purposes of establishing a convention, the molar activity coefficient of the solvent is set equal to the molality-based activity coefficient of the solvent:

\[ \gamma_o = \gamma_o^\triangle \]

Derived classes don't need to overload this function. This function is handled at this level.

Parameters
acOutput vector containing the mole-fraction based activity coefficients. length: m_kk.

Reimplemented from ThermoPhase.

Definition at line 201 of file MolalityVPSSTP.cpp.

◆ getMolalityActivityCoefficients()

void getMolalityActivityCoefficients ( double *  acMolality) const
virtual

Get the array of non-dimensional molality based activity coefficients at the current solution temperature, pressure, and solution concentration.

See Denbigh p. 278 [5] for a thorough discussion. This method must be overridden in classes which derive from MolalityVPSSTP. This function takes over from the molar-based activity coefficient calculation, getActivityCoefficients(), in derived classes.

These molality based activity coefficients are scaled according to the current pH scale. See the Eq3/6 manual for details.

Activity coefficients for species k may be altered between scales s1 to s2 using the following formula

\[ \ln(\gamma_k^{s2}) = \ln(\gamma_k^{s1}) + \frac{z_k}{z_j} \left( \ln(\gamma_j^{s2}) - \ln(\gamma_j^{s1}) \right) \]

where j is any one species. For the NBS scale, j is equal to the Cl- species and

\[ \ln(\gamma_{Cl-}^{s2}) = \frac{-A_{\phi} \sqrt{I}}{1.0 + 1.5 \sqrt{I}} \]

Parameters
acMolalityOutput vector containing the molality based activity coefficients. length: m_kk.

Reimplemented in DebyeHuckel, and IdealMolalSoln.

Definition at line 210 of file MolalityVPSSTP.cpp.

◆ osmoticCoefficient()

double osmoticCoefficient ( ) const
virtual

Calculate the osmotic coefficient.

\[ \phi = \frac{- \ln(a_o)}{\tilde{M}_o \sum_{i \ne o} m_i} \]

Note there are a few of definitions of the osmotic coefficient floating around. We use the one defined in (Activity Coefficients in Electrolyte Solutions, K. S. Pitzer CRC Press, Boca Raton, 1991, p. 85, Eqn. 28). This definition is most clearly related to theoretical calculation.

units = dimensionless

Definition at line 216 of file MolalityVPSSTP.cpp.

◆ addSpecies()

bool addSpecies ( shared_ptr< Species spec)
overridevirtual

Add a Species to this Phase.

Returns true if the species was successfully added, or false if the species was ignored.

Derived classes which need to size arrays according to the number of species should overload this method. The derived class implementation should call the base class method, and, if this returns true (indicating that the species has been added), adjust their array sizes accordingly.

See also
ignoreUndefinedElements addUndefinedElements throwUndefinedElements

Reimplemented from Phase.

Definition at line 343 of file MolalityVPSSTP.cpp.

◆ initThermo()

void initThermo ( )
overridevirtual

Initialize the ThermoPhase object after all species have been set up.

This method is provided to allow subclasses to perform any initialization required after all species have been added. For example, it might be used to resize internal work arrays that must have an entry for each species. The base class implementation does nothing, and subclasses that do not require initialization do not need to overload this method. Derived classes which do override this function should call their parent class's implementation of this function as their last action.

When importing from an AnyMap phase description (or from a YAML file), setupPhase() adds all the species, stores the input data in m_input, and then calls this method to set model parameters from the data stored in m_input.

Reimplemented from ThermoPhase.

Definition at line 269 of file MolalityVPSSTP.cpp.

◆ setState_TPM() [1/3]

void setState_TPM ( double  t,
double  p,
const double *const  molalities 
)

Set the temperature (K), pressure (Pa), and molalities (gmol kg-1) of the solutes.

Parameters
tTemperature (K)
pPressure (Pa)
molalitiesInput vector of molalities of the solutes. Length: m_kk.

Definition at line 234 of file MolalityVPSSTP.cpp.

◆ setState_TPM() [2/3]

void setState_TPM ( double  t,
double  p,
const Composition m 
)

Set the temperature (K), pressure (Pa), and molalities.

Parameters
tTemperature (K)
pPressure (Pa)
mComposition containing the molalities

Definition at line 240 of file MolalityVPSSTP.cpp.

◆ setState_TPM() [3/3]

void setState_TPM ( double  t,
double  p,
const string &  m 
)

Set the temperature (K), pressure (Pa), and molalities.

Parameters
tTemperature (K)
pPressure (Pa)
mString which gets translated into a composition map for the molalities of the solutes.

Definition at line 246 of file MolalityVPSSTP.cpp.

◆ setState()

void setState ( const AnyMap state)
overridevirtual

Set the state using an AnyMap containing any combination of properties supported by the thermodynamic model.

Accepted keys are:

  • X (mole fractions)
  • Y (mass fractions)
  • T or temperature
  • P or pressure [Pa]
  • H or enthalpy [J/kg]
  • U or internal-energy [J/kg]
  • S or entropy [J/kg/K]
  • V or specific-volume [m^3/kg]
  • D or density [kg/m^3]

Composition can be specified as either an AnyMap of species names to values or as a composition string. All other values can be given as floating point values in Cantera's default units, or as strings with the units specified, which will be converted using the Units class.

If no thermodynamic property pair is given, or only one of temperature or pressure is given, then 298.15 K and 101325 Pa will be used as necessary to fully set the state.

Additionally uses the keys molalities or M to set the molalities.

Reimplemented from ThermoPhase.

Definition at line 252 of file MolalityVPSSTP.cpp.

◆ getdlnActCoeffdlnN()

void getdlnActCoeffdlnN ( const size_t  ld,
double *const  dlnActCoeffdlnN 
)
inlineoverridevirtual

Get the array of derivatives of the log activity coefficients with respect to the log of the species mole numbers.

Implementations should take the derivative of the logarithm of the activity coefficient with respect to a species log mole number (with all other species mole numbers held constant). The default treatment in the ThermoPhase object is to set this vector to zero.

units = 1 / kmol

dlnActCoeffdlnN[ ld * k + m] will contain the derivative of log act_coeff for the m-th species with respect to the number of moles of the k-th species.

\[ \frac{d \ln(\gamma_m) }{d \ln( n_k ) }\Bigg|_{n_i} \]

When implemented, this method is used within the VCS equilibrium solver to calculate the Jacobian elements, which accelerates convergence of the algorithm.

Parameters
ldNumber of rows in the matrix
dlnActCoeffdlnNOutput vector of derivatives of the log Activity Coefficients. length = m_kk * m_kk

Reimplemented from ThermoPhase.

Definition at line 535 of file MolalityVPSSTP.h.

◆ report()

string report ( bool  show_thermo = true,
double  threshold = 1e-14 
) const
overridevirtual

returns a summary of the state of the phase as a string

Parameters
show_thermoIf true, extra information is printed out about the thermodynamic state of the system.
thresholdShow information about species with mole fractions greater than threshold.

Reimplemented from ThermoPhase.

Definition at line 357 of file MolalityVPSSTP.cpp.

◆ getUnscaledMolalityActivityCoefficients()

void getUnscaledMolalityActivityCoefficients ( double *  acMolality) const
protectedvirtual

Get the array of unscaled non-dimensional molality based activity coefficients at the current solution temperature, pressure, and solution concentration.

See Denbigh p. 278 [5] for a thorough discussion. This method must be overridden in classes which derive from MolalityVPSSTP. This function takes over from the molar-based activity coefficient calculation, getActivityCoefficients(), in derived classes.

Parameters
acMolalityOutput vector containing the molality based activity coefficients. length: m_kk.

Reimplemented in HMWSoln.

Definition at line 277 of file MolalityVPSSTP.cpp.

◆ applyphScale()

void applyphScale ( double *  acMolality) const
protectedvirtual

Apply the current phScale to a set of activity Coefficients or activities.

See the Eq3/6 Manual for a thorough discussion.

Parameters
acMolalityinput/Output vector containing the molality based activity coefficients. length: m_kk.

Reimplemented in HMWSoln.

Definition at line 282 of file MolalityVPSSTP.cpp.

◆ findCLMIndex()

size_t findCLMIndex ( ) const
private

Returns the index of the Cl- species.

The Cl- species is special in the sense that its single ion molality- based activity coefficient is used in the specification of the pH scale for single ions. Therefore, we need to know what species index is Cl-. If the species isn't in the species list then this routine returns -1, and we can't use the NBS pH scale.

Right now we use a restrictive interpretation. The species must be named "Cl-". It must consist of exactly one Cl and one E atom.

Definition at line 287 of file MolalityVPSSTP.cpp.

Member Data Documentation

◆ m_pHScalingType

int m_pHScalingType = PHSCALE_PITZER
protected

Scaling to be used for output of single-ion species activity coefficients.

Index of the species to be used in the single-ion scaling law. This is the identity of the Cl- species for the PHSCALE_NBS scaling. Either PHSCALE_PITZER or PHSCALE_NBS

Definition at line 588 of file MolalityVPSSTP.h.

◆ m_indexCLM

size_t m_indexCLM = npos
protected

Index of the phScale species.

Index of the species to be used in the single-ion scaling law. This is the identity of the Cl- species for the PHSCALE_NBS scaling

Definition at line 595 of file MolalityVPSSTP.h.

◆ m_weightSolvent

double m_weightSolvent = 18.01528
protected

Molecular weight of the Solvent.

Definition at line 598 of file MolalityVPSSTP.h.

◆ m_xmolSolventMIN

double m_xmolSolventMIN = 0.01
protected

In any molality implementation, it makes sense to have a minimum solvent mole fraction requirement, since the implementation becomes singular in the xmolSolvent=0 limit.

The default is to set it to 0.01. We then modify the molality definition to ensure that molal_solvent = 0 when xmol_solvent = 0.

Definition at line 607 of file MolalityVPSSTP.h.

◆ m_Mnaught

double m_Mnaught = 18.01528E-3
protected

This is the multiplication factor that goes inside log expressions involving the molalities of species.

It's equal to Wt_0 / 1000, where Wt_0 = weight of solvent (kg/kmol)

Definition at line 612 of file MolalityVPSSTP.h.

◆ m_molalities

vector<double> m_molalities
mutableprotected

Current value of the molalities of the species in the phase.

Note this vector is a mutable quantity. units are (kg/kmol)

Definition at line 616 of file MolalityVPSSTP.h.


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