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Cantera
3.1.0a1
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Cantera
3.1.0a1
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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>
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.
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.
Definition at line 226 of file MolalityVPSSTP.h.
Public Member Functions | |
| MolalityVPSSTP () | |
| Default Constructor. More... | |
| 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. More... | |
| void | setState_TPM (double t, double p, const Composition &m) |
| Set the temperature (K), pressure (Pa), and molalities. More... | |
| void | setState_TPM (double t, double p, const string &m) |
| Set the temperature (K), pressure (Pa), and molalities. More... | |
| void | setState (const AnyMap &state) override |
| Set the state using an AnyMap containing any combination of properties supported by the thermodynamic model. More... | |
| 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. More... | |
| string | report (bool show_thermo=true, double threshold=1e-14) const override |
| returns a summary of the state of the phase as a string More... | |
Utilities | |
| string | phaseOfMatter () const override |
| String indicating the mechanical phase of the matter in this Phase. More... | |
| void | setpHScale (const int pHscaleType) |
| Set the pH scale, which determines the scale for single-ion activity coefficients. More... | |
| int | pHScale () const |
| Reports the pH scale, which determines the scale for single-ion activity coefficients. More... | |
Utilities for Solvent ID and Molality | |
| void | setMoleFSolventMin (double xmolSolventMIN) |
| Sets the minimum mole fraction in the molality formulation. More... | |
| double | moleFSolventMin () const |
| Returns the minimum mole fraction in the molality formulation. More... | |
| void | calcMolalities () const |
| Calculates the molality of all species and stores the result internally. More... | |
| void | getMolalities (double *const molal) const |
| This function will return the molalities of the species. More... | |
| void | setMolalities (const double *const molal) |
| Set the molalities of the solutes in a phase. More... | |
| void | setMolalitiesByName (const Composition &xMap) |
| Set the molalities of a phase. More... | |
| void | setMolalitiesByName (const string &name) |
| Set the molalities of a phase. More... | |
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. More... | |
| void | getActivityConcentrations (double *c) const override |
| This method returns an array of generalized concentrations. More... | |
| double | standardConcentration (size_t k=0) const override |
| Return the standard concentration for the kth species. More... | |
| 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. More... | |
| void | getActivityCoefficients (double *ac) const override |
| Get the array of non-dimensional activity coefficients at the current solution temperature, pressure, and solution concentration. More... | |
| 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. More... | |
| virtual double | osmoticCoefficient () const |
| Calculate the osmotic coefficient. More... | |
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. More... | |
| void | initThermo () override |
| Initialize the ThermoPhase object after all species have been set up. More... | |
 Public Member Functions inherited from VPStandardStateTP | |
| void | setTemperature (const double temp) override |
| Set the temperature of the phase. More... | |
| void | setPressure (double p) override |
| Set the internally stored pressure (Pa) at constant temperature and composition. More... | |
| void | setState_TP (double T, double pres) override |
| Set the temperature and pressure at the same time. More... | |
| double | pressure () const override |
| Returns the current pressure of the phase. More... | |
| virtual void | updateStandardStateThermo () const |
| Updates the standard state thermodynamic functions at the current T and P of the solution. More... | |
| double | minTemp (size_t k=npos) const override |
| Minimum temperature for which the thermodynamic data for the species or phase are valid. More... | |
| double | maxTemp (size_t k=npos) const override |
| Maximum temperature for which the thermodynamic data for the species are valid. More... | |
| PDSS * | providePDSS (size_t k) |
| const PDSS * | providePDSS (size_t k) const |
| VPStandardStateTP () | |
| Constructor. More... | |
| ~VPStandardStateTP () override | |
| bool | isCompressible () const override |
| Return whether phase represents a compressible substance. More... | |
| 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. More... | |
| 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. More... | |
| 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. More... | |
| 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. More... | |
| 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. More... | |
| 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. More... | |
| 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. More... | |
| 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. More... | |
| void | getStandardVolumes (double *vol) const override |
| Get the molar volumes of the species standard states at the current T and P of the solution. More... | |
| virtual const vector< double > & | getStandardVolumes () const |
| void | initThermo () override |
| Initialize the ThermoPhase object after all species have been set up. More... | |
| 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. More... | |
| bool | addSpecies (shared_ptr< Species > spec) override |
| Add a Species to this Phase. More... | |
| void | installPDSS (size_t k, unique_ptr< PDSS > &&pdss) |
| Install a PDSS object for species k More... | |
| virtual bool | addSpecies (shared_ptr< Species > spec) |
| Add a Species to this Phase. More... | |
| 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. More... | |
| 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. More... | |
| 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. More... | |
| 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. More... | |
| 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. More... | |
| 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. More... | |
| Public Member Functions inherited from ThermoPhase | |
| ThermoPhase ()=default | |
| Constructor. More... | |
| double | RT () const |
| Return the Gas Constant multiplied by the current temperature. More... | |
| double | equivalenceRatio () const |
| Compute the equivalence ratio for the current mixture from available oxygen and required oxygen. More... | |
| string | type () const override |
| String indicating the thermodynamic model implemented. More... | |
| virtual bool | isIdeal () const |
| Boolean indicating whether phase is ideal. More... | |
| virtual double | refPressure () const |
| Returns the reference pressure in Pa. More... | |
| double | Hf298SS (const size_t k) const |
| Report the 298 K Heat of Formation of the standard state of one species (J kmol-1) More... | |
| 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) More... | |
| virtual void | resetHf298 (const size_t k=npos) |
| Restore the original heat of formation of one or more species. More... | |
| bool | chargeNeutralityNecessary () const |
| Returns the chargeNeutralityNecessity boolean. More... | |
| virtual double | enthalpy_mole () const |
| Molar enthalpy. Units: J/kmol. More... | |
| virtual double | intEnergy_mole () const |
| Molar internal energy. Units: J/kmol. More... | |
| virtual double | entropy_mole () const |
| Molar entropy. Units: J/kmol/K. More... | |
| virtual double | gibbs_mole () const |
| Molar Gibbs function. Units: J/kmol. More... | |
| virtual double | cp_mole () const |
| Molar heat capacity at constant pressure. Units: J/kmol/K. More... | |
| virtual double | cv_mole () const |
| Molar heat capacity at constant volume. Units: J/kmol/K. More... | |
| virtual double | isothermalCompressibility () const |
| Returns the isothermal compressibility. Units: 1/Pa. More... | |
| virtual double | thermalExpansionCoeff () const |
| Return the volumetric thermal expansion coefficient. Units: 1/K. More... | |
| virtual double | soundSpeed () const |
| Return the speed of sound. Units: m/s. More... | |
| void | setElectricPotential (double v) |
| Set the electric potential of this phase (V). More... | |
| double | electricPotential () const |
| Returns the electric potential of this phase (V). More... | |
| virtual Units | standardConcentrationUnits () const |
| Returns the units of the "standard concentration" for this phase. More... | |
| virtual double | logStandardConc (size_t k=0) const |
| Natural logarithm of the standard concentration of the kth species. More... | |
| 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. More... | |
| virtual void | getChemPotentials (double *mu) const |
| Get the species chemical potentials. Units: J/kmol. More... | |
| void | getElectrochemPotentials (double *mu) const |
| Get the species electrochemical potentials. More... | |
| virtual void | getPartialMolarEnthalpies (double *hbar) const |
| Returns an array of partial molar enthalpies for the species in the mixture. More... | |
| virtual void | getPartialMolarEntropies (double *sbar) const |
| Returns an array of partial molar entropies of the species in the solution. More... | |
| virtual void | getPartialMolarIntEnergies (double *ubar) const |
| Return an array of partial molar internal energies for the species in the mixture. More... | |
| virtual void | getPartialMolarCp (double *cpbar) const |
| Return an array of partial molar heat capacities for the species in the mixture. More... | |
| virtual void | getPartialMolarVolumes (double *vbar) const |
| Return an array of partial molar volumes for the species in the mixture. More... | |
| 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. More... | |
| double | enthalpy_mass () const |
| Specific enthalpy. Units: J/kg. More... | |
| double | intEnergy_mass () const |
| Specific internal energy. Units: J/kg. More... | |
| double | entropy_mass () const |
| Specific entropy. Units: J/kg/K. More... | |
| double | gibbs_mass () const |
| Specific Gibbs function. Units: J/kg. More... | |
| double | cp_mass () const |
| Specific heat at constant pressure. Units: J/kg/K. More... | |
| double | cv_mass () const |
| Specific heat at constant volume. Units: J/kg/K. More... | |
| virtual void | setState_TPX (double t, double p, const double *x) |
| Set the temperature (K), pressure (Pa), and mole fractions. More... | |
| virtual void | setState_TPX (double t, double p, const Composition &x) |
| Set the temperature (K), pressure (Pa), and mole fractions. More... | |
| virtual void | setState_TPX (double t, double p, const string &x) |
| Set the temperature (K), pressure (Pa), and mole fractions. More... | |
| 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. More... | |
| 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. More... | |
| 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. More... | |
| 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. More... | |
| 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). More... | |
| virtual void | setState_SP (double s, double p, double tol=1e-9) |
| Set the specific entropy (J/kg/K) and pressure (Pa). More... | |
| 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). More... | |
| virtual void | setState_ST (double s, double t, double tol=1e-9) |
| Set the specific entropy (J/kg/K) and temperature (K). More... | |
| virtual void | setState_TV (double t, double v, double tol=1e-9) |
| Set the temperature (K) and specific volume (m^3/kg). More... | |
| virtual void | setState_PV (double p, double v, double tol=1e-9) |
| Set the pressure (Pa) and specific volume (m^3/kg). More... | |
| virtual void | setState_UP (double u, double p, double tol=1e-9) |
| Set the specific internal energy (J/kg) and pressure (Pa). More... | |
| 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) More... | |
| virtual void | setState_TH (double t, double h, double tol=1e-9) |
| Set the temperature (K) and the specific enthalpy (J/kg) More... | |
| 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) More... | |
| virtual void | setState_DP (double rho, double p) |
| Set the density (kg/m**3) and pressure (Pa) at constant composition. More... | |
| 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) More... | |
| 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) More... | |
| 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) More... | |
| 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. More... | |
| 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. More... | |
| 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. More... | |
| void | setEquivalenceRatio (double phi, const double *fuelComp, const double *oxComp, ThermoBasis basis=ThermoBasis::molar) |
| Set the mixture composition according to the equivalence ratio. More... | |
| void | setEquivalenceRatio (double phi, const string &fuelComp, const string &oxComp, ThermoBasis basis=ThermoBasis::molar) |
| Set the mixture composition according to the equivalence ratio. More... | |
| void | setEquivalenceRatio (double phi, const Composition &fuelComp, const Composition &oxComp, ThermoBasis basis=ThermoBasis::molar) |
| Set the mixture composition according to the equivalence ratio. More... | |
| 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. More... | |
| 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. More... | |
| 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. More... | |
| 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. More... | |
| 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. More... | |
| 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. More... | |
| 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. More... | |
| virtual void | setToEquilState (const double *mu_RT) |
| This method is used by the ChemEquil equilibrium solver. More... | |
| virtual bool | compatibleWithMultiPhase () const |
| Indicates whether this phase type can be used with class MultiPhase for equilibrium calculations. More... | |
| virtual double | critTemperature () const |
| Critical temperature (K). More... | |
| virtual double | critPressure () const |
| Critical pressure (Pa). More... | |
| virtual double | critVolume () const |
| Critical volume (m3/kmol). More... | |
| virtual double | critCompressibility () const |
| Critical compressibility (unitless). More... | |
| virtual double | critDensity () const |
| Critical density (kg/m3). More... | |
| virtual double | satTemperature (double p) const |
| Return the saturation temperature given the pressure. More... | |
| virtual double | satPressure (double t) |
| Return the saturation pressure given the temperature. More... | |
| virtual double | vaporFraction () const |
| Return the fraction of vapor at the current conditions. More... | |
| virtual void | setState_Tsat (double t, double x) |
| Set the state to a saturated system at a particular temperature. More... | |
| virtual void | setState_Psat (double p, double x) |
| Set the state to a saturated system at a particular pressure. More... | |
| void | setState_TPQ (double T, double P, double Q) |
| Set the temperature, pressure, and vapor fraction (quality). More... | |
| void | modifySpecies (size_t k, shared_ptr< Species > spec) override |
| Modify the thermodynamic data associated with a species. More... | |
| virtual MultiSpeciesThermo & | speciesThermo (int k=-1) |
| Return a changeable reference to the calculation manager for species reference-state thermodynamic properties. More... | |
| virtual const MultiSpeciesThermo & | speciesThermo (int k=-1) const |
| void | initThermoFile (const string &inputFile, const string &id) |
| Initialize a ThermoPhase object using an input file. More... | |
| virtual void | setParameters (const AnyMap &phaseNode, const AnyMap &rootNode=AnyMap()) |
| Set equation of state parameters from an AnyMap phase description. More... | |
| 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. More... | |
| const AnyMap & | input () const |
| Access input data associated with the phase description. More... | |
| AnyMap & | input () |
| 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. More... | |
| virtual void | getdlnActCoeffdlnX_diag (double *dlnActCoeffdlnX_diag) const |
| Get the array of ln mole fraction derivatives of the log activity coefficients - diagonal component only. More... | |
| virtual void | getdlnActCoeffdlnN_diag (double *dlnActCoeffdlnN_diag) const |
| Get the array of log species mole number derivatives of the log activity coefficients. More... | |
| virtual void | getdlnActCoeffdlnN_numderiv (const size_t ld, double *const dlnActCoeffdlnN) |
| Public Member Functions inherited from Phase | |
| Phase ()=default | |
| Default constructor. More... | |
| Phase (const Phase &)=delete | |
| Phase & | operator= (const Phase &)=delete |
| virtual bool | isPure () const |
| Return whether phase represents a pure (single species) substance. More... | |
| virtual bool | hasPhaseTransition () const |
| Return whether phase represents a substance with phase transitions. More... | |
| virtual map< string, size_t > | nativeState () const |
| Return a map of properties defining the native state of a substance. More... | |
| string | nativeMode () const |
| Return string acronym representing the native state of a Phase. More... | |
| virtual vector< string > | fullStates () const |
| Return a vector containing full states defining a phase. More... | |
| virtual vector< string > | partialStates () const |
| Return a vector of settable partial property sets within a phase. More... | |
| virtual size_t | stateSize () const |
| Return size of vector defining internal state of the phase. More... | |
| void | saveState (vector< double > &state) const |
| Save the current internal state of the phase. More... | |
| virtual void | saveState (size_t lenstate, double *state) const |
| Write to array 'state' the current internal state. More... | |
| void | restoreState (const vector< double > &state) |
| Restore a state saved on a previous call to saveState. More... | |
| virtual void | restoreState (size_t lenstate, const double *state) |
| Restore the state of the phase from a previously saved state vector. More... | |
| double | molecularWeight (size_t k) const |
Molecular weight of species k. More... | |
| void | getMolecularWeights (double *weights) const |
| Copy the vector of molecular weights into array weights. More... | |
| const vector< double > & | molecularWeights () const |
| Return a const reference to the internal vector of molecular weights. More... | |
| const vector< double > & | inverseMolecularWeights () const |
| Return a const reference to the internal vector of molecular weights. More... | |
| void | getCharges (double *charges) const |
| Copy the vector of species charges into array charges. More... | |
| virtual void | setMolesNoTruncate (const double *const N) |
| Set the state of the object with moles in [kmol]. More... | |
| double | elementalMassFraction (const size_t m) const |
| Elemental mass fraction of element m. More... | |
| double | elementalMoleFraction (const size_t m) const |
| Elemental mole fraction of element m. More... | |
| 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. More... | |
| double | chargeDensity () const |
| Charge density [C/m^3]. More... | |
| size_t | nDim () const |
| Returns the number of spatial dimensions (1, 2, or 3) More... | |
| void | setNDim (size_t ndim) |
| Set the number of spatial dimensions (1, 2, or 3). More... | |
| virtual bool | ready () const |
| Returns a bool indicating whether the object is ready for use. More... | |
| int | stateMFNumber () const |
| Return the State Mole Fraction Number. More... | |
| bool | caseSensitiveSpecies () const |
Returns true if case sensitive species names are enforced. More... | |
| void | setCaseSensitiveSpecies (bool cflag=true) |
| Set flag that determines whether case sensitive species are enforced in look-up operations, for example speciesIndex. More... | |
| 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. More... | |
| void | massFractionsToMoleFractions (const double *Y, double *X) const |
| Converts a mixture composition from mole fractions to mass fractions. More... | |
| void | moleFractionsToMassFractions (const double *X, double *Y) const |
| Converts a mixture composition from mass fractions to mole fractions. More... | |
| string | name () const |
| Return the name of the phase. More... | |
| void | setName (const string &nm) |
| Sets the string name for the phase. More... | |
| string | elementName (size_t m) const |
| Name of the element with index m. More... | |
| size_t | elementIndex (const string &name) const |
| Return the index of element named 'name'. More... | |
| const vector< string > & | elementNames () const |
| Return a read-only reference to the vector of element names. More... | |
| double | atomicWeight (size_t m) const |
| Atomic weight of element m. More... | |
| double | entropyElement298 (size_t m) const |
| Entropy of the element in its standard state at 298 K and 1 bar. More... | |
| int | atomicNumber (size_t m) const |
| Atomic number of element m. More... | |
| int | elementType (size_t m) const |
| Return the element constraint type Possible types include: More... | |
| int | changeElementType (int m, int elem_type) |
| Change the element type of the mth constraint Reassigns an element type. More... | |
| const vector< double > & | atomicWeights () const |
| Return a read-only reference to the vector of atomic weights. More... | |
| size_t | nElements () const |
| Number of elements. More... | |
| void | checkElementIndex (size_t m) const |
| Check that the specified element index is in range. More... | |
| void | checkElementArraySize (size_t mm) const |
| Check that an array size is at least nElements(). More... | |
| double | nAtoms (size_t k, size_t m) const |
Number of atoms of element m in species k. More... | |
| size_t | speciesIndex (const string &name) const |
| Returns the index of a species named 'name' within the Phase object. More... | |
| string | speciesName (size_t k) const |
| Name of the species with index k. More... | |
| const vector< string > & | speciesNames () const |
| Return a const reference to the vector of species names. More... | |
| size_t | nSpecies () const |
| Returns the number of species in the phase. More... | |
| void | checkSpeciesIndex (size_t k) const |
| Check that the specified species index is in range. More... | |
| void | checkSpeciesArraySize (size_t kk) const |
| Check that an array size is at least nSpecies(). More... | |
| void | setMoleFractionsByName (const Composition &xMap) |
| Set the species mole fractions by name. More... | |
| void | setMoleFractionsByName (const string &x) |
| Set the mole fractions of a group of species by name. More... | |
| void | setMassFractionsByName (const Composition &yMap) |
| Set the species mass fractions by name. More... | |
| void | setMassFractionsByName (const string &x) |
| Set the species mass fractions by name. More... | |
| void | setState_TD (double t, double rho) |
| Set the internally stored temperature (K) and density (kg/m^3) More... | |
| Composition | getMoleFractionsByName (double threshold=0.0) const |
| Get the mole fractions by name. More... | |
| double | moleFraction (size_t k) const |
| Return the mole fraction of a single species. More... | |
| double | moleFraction (const string &name) const |
| Return the mole fraction of a single species. More... | |
| Composition | getMassFractionsByName (double threshold=0.0) const |
| Get the mass fractions by name. More... | |
| double | massFraction (size_t k) const |
| Return the mass fraction of a single species. More... | |
| double | massFraction (const string &name) const |
| Return the mass fraction of a single species. More... | |
| void | getMoleFractions (double *const x) const |
| Get the species mole fraction vector. More... | |
| virtual void | setMoleFractions (const double *const x) |
| Set the mole fractions to the specified values. More... | |
| virtual void | setMoleFractions_NoNorm (const double *const x) |
| Set the mole fractions to the specified values without normalizing. More... | |
| void | getMassFractions (double *const y) const |
| Get the species mass fractions. More... | |
| const double * | massFractions () const |
| Return a const pointer to the mass fraction array. More... | |
| virtual void | setMassFractions (const double *const y) |
| Set the mass fractions to the specified values and normalize them. More... | |
| virtual void | setMassFractions_NoNorm (const double *const y) |
| Set the mass fractions to the specified values without normalizing. More... | |
| virtual void | getConcentrations (double *const c) const |
| Get the species concentrations (kmol/m^3). More... | |
| virtual double | concentration (const size_t k) const |
| Concentration of species k. More... | |
| virtual void | setConcentrations (const double *const conc) |
| Set the concentrations to the specified values within the phase. More... | |
| virtual void | setConcentrationsNoNorm (const double *const conc) |
| Set the concentrations without ignoring negative concentrations. More... | |
| double | temperature () const |
| Temperature (K). More... | |
| virtual double | electronTemperature () const |
| Electron Temperature (K) More... | |
| virtual double | density () const |
| Density (kg/m^3). More... | |
| virtual double | molarDensity () const |
| Molar density (kmol/m^3). More... | |
| virtual double | molarVolume () const |
| Molar volume (m^3/kmol). More... | |
| virtual void | setDensity (const double density_) |
| Set the internally stored density (kg/m^3) of the phase. More... | |
| virtual void | setElectronTemperature (double etemp) |
| Set the internally stored electron temperature of the phase (K). More... | |
| double | mean_X (const double *const Q) const |
| Evaluate the mole-fraction-weighted mean of an array Q. More... | |
| double | mean_X (const vector< double > &Q) const |
| Evaluate the mole-fraction-weighted mean of an array Q. More... | |
| double | meanMolecularWeight () const |
| The mean molecular weight. Units: (kg/kmol) More... | |
| double | sum_xlogx () const |
| Evaluate \( \sum_k X_k \ln X_k \). More... | |
| 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. More... | |
| void | addSpeciesAlias (const string &name, const string &alias) |
| Add a species alias (that is, a user-defined alternative species name). More... | |
| virtual vector< string > | findIsomers (const Composition &compMap) const |
| Return a vector with isomers names matching a given composition map. More... | |
| virtual vector< string > | findIsomers (const string &comp) const |
| Return a vector with isomers names matching a given composition string. More... | |
| shared_ptr< Species > | species (const string &name) const |
| Return the Species object for the named species. More... | |
| shared_ptr< Species > | species (size_t k) const |
| Return the Species object for species whose index is k. More... | |
| void | ignoreUndefinedElements () |
| Set behavior when adding a species containing undefined elements to just skip the species. More... | |
| void | addUndefinedElements () |
| Set behavior when adding a species containing undefined elements to add those elements to the phase. More... | |
| void | throwUndefinedElements () |
| Set the behavior when adding a species containing undefined elements to throw an exception. More... | |
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. More... | |
| virtual void | applyphScale (double *acMolality) const |
| Apply the current phScale to a set of activity Coefficients or activities. More... | |
| 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. More... | |
| virtual void | _updateStandardStateThermo () const |
| Updates the standard state thermodynamic functions at the current T and P of the solution. More... | |
| void | invalidateCache () override |
| Invalidate any cached values which are normally updated only when a change in state is detected. More... | |
| 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. More... | |
| Protected Member Functions inherited from Phase | |
| void | assertCompressible (const string &setter) const |
| Ensure that phase is compressible. More... | |
| void | assignDensity (const double density_) |
| Set the internally stored constant density (kg/m^3) of the phase. More... | |
| void | setMolecularWeight (const int k, const double mw) |
| Set the molecular weight of a single species to a given value. More... | |
| virtual void | compositionChanged () |
| Apply changes to the state which are needed after the composition changes. More... | |
Protected Attributes | |
| int | m_pHScalingType = PHSCALE_PITZER |
| Scaling to be used for output of single-ion species activity coefficients. More... | |
| size_t | m_indexCLM = npos |
| Index of the phScale species. More... | |
| double | m_weightSolvent = 18.01528 |
| Molecular weight of the Solvent. More... | |
| 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. More... | |
| double | m_Mnaught = 18.01528E-3 |
| This is the multiplication factor that goes inside log expressions involving the molalities of species. More... | |
| vector< double > | m_molalities |
| Current value of the molalities of the species in the phase. More... | |
| Protected Attributes inherited from VPStandardStateTP | |
| double | m_Pcurrent = OneAtm |
| Current value of the pressure - state variable. More... | |
| double | m_minTemp = 0.0 |
| The minimum temperature at which data for all species is valid. More... | |
| double | m_maxTemp = BigNumber |
| The maximum temperature at which data for all species is valid. More... | |
| double | m_Tlast_ss = -1.0 |
| The last temperature at which the standard state thermodynamic properties were calculated at. More... | |
| double | m_Plast_ss = -1.0 |
| The last pressure at which the Standard State thermodynamic properties were calculated at. More... | |
| vector< unique_ptr< PDSS > > | m_PDSS_storage |
| Storage for the PDSS objects for the species. More... | |
| vector< double > | m_h0_RT |
| Vector containing the species reference enthalpies at T = m_tlast and P = p_ref. More... | |
| vector< double > | m_cp0_R |
| Vector containing the species reference constant pressure heat capacities at T = m_tlast and P = p_ref. More... | |
| vector< double > | m_g0_RT |
| Vector containing the species reference Gibbs functions at T = m_tlast and P = p_ref. More... | |
| vector< double > | m_s0_R |
| Vector containing the species reference entropies at T = m_tlast and P = p_ref. More... | |
| vector< double > | m_V0 |
| Vector containing the species reference molar volumes. More... | |
| vector< double > | m_hss_RT |
| Vector containing the species Standard State enthalpies at T = m_tlast and P = m_plast. More... | |
| vector< double > | m_cpss_R |
| Vector containing the species Standard State constant pressure heat capacities at T = m_tlast and P = m_plast. More... | |
| vector< double > | m_gss_RT |
| Vector containing the species Standard State Gibbs functions at T = m_tlast and P = m_plast. More... | |
| vector< double > | m_sss_R |
| Vector containing the species Standard State entropies at T = m_tlast and P = m_plast. More... | |
| vector< double > | m_Vss |
| Vector containing the species standard state volumes at T = m_tlast and P = m_plast. More... | |
| Protected Attributes inherited from ThermoPhase | |
| MultiSpeciesThermo | m_spthermo |
| Pointer to the calculation manager for species reference-state thermodynamic properties. More... | |
| AnyMap | m_input |
| Data supplied via setParameters. More... | |
| double | m_phi = 0.0 |
| Stored value of the electric potential for this phase. Units are Volts. More... | |
| bool | m_chargeNeutralityNecessary = false |
| Boolean indicating whether a charge neutrality condition is a necessity. More... | |
| int | m_ssConvention = cSS_CONVENTION_TEMPERATURE |
| Contains the standard state convention. More... | |
| double | m_tlast = 0.0 |
| last value of the temperature processed by reference state More... | |
| Protected Attributes inherited from Phase | |
| ValueCache | m_cache |
| Cached for saved calculations within each ThermoPhase. More... | |
| size_t | m_kk = 0 |
| Number of species in the phase. More... | |
| size_t | m_ndim = 3 |
| Dimensionality of the phase. More... | |
| vector< double > | m_speciesComp |
| Atomic composition of the species. More... | |
| vector< double > | m_speciesCharge |
| Vector of species charges. length m_kk. More... | |
| map< string, shared_ptr< Species > > | m_species |
| UndefElement::behavior | m_undefinedElementBehavior = UndefElement::add |
| Flag determining behavior when adding species with an undefined element. More... | |
| bool | m_caseSensitiveSpecies = false |
| Flag determining whether case sensitive species names are enforced. More... | |
Private Member Functions | |
| size_t | findCLMIndex () const |
| Returns the index of the Cl- species. More... | |
| 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.
|
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.
| 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.
| pHscaleType | Integer representing the pHscale |
Definition at line 31 of file MolalityVPSSTP.cpp.
| 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.
Definition at line 40 of file MolalityVPSSTP.cpp.
| 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.
| xmolSolventMIN | Input double containing the minimum mole fraction |
Definition at line 45 of file MolalityVPSSTP.cpp.
| double moleFSolventMin | ( | ) | const |
Returns the minimum mole fraction in the molality formulation.
Definition at line 55 of file MolalityVPSSTP.cpp.
| 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
Definition at line 60 of file MolalityVPSSTP.cpp.
| 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
| molal | Output vector of molalities. Length: m_kk. |
Definition at line 70 of file MolalityVPSSTP.cpp.
| 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
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 \( X_o^{min} \).
| molal | Input vector of molalities. Length: m_kk. |
Definition at line 78 of file MolalityVPSSTP.cpp.
| 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.
| xMap | Composition Map containing the molalities. |
Definition at line 105 of file MolalityVPSSTP.cpp.
| 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.
| name | String containing the information for a composition map. |
Definition at line 173 of file MolalityVPSSTP.cpp.
|
overridevirtual |
We set the convention to molality here.
Reimplemented from ThermoPhase.
Definition at line 181 of file MolalityVPSSTP.cpp.
|
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.
| c | Output 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.
|
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.
| k | Optional parameter indicating the species. The default is to assume this refers to species 0. |
Reimplemented from ThermoPhase.
Definition at line 191 of file MolalityVPSSTP.cpp.
|
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.
| ac | Output vector of molality-based activities. Length: m_kk. |
Reimplemented from ThermoPhase.
Definition at line 196 of file MolalityVPSSTP.cpp.
|
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.
| ac | Output vector containing the mole-fraction based activity coefficients. length: m_kk. |
Reimplemented from ThermoPhase.
Definition at line 201 of file MolalityVPSSTP.cpp.
|
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
\[ \ln(\gamma_{Cl-}^{s2}) = \frac{-A_{\phi} \sqrt{I}}{1.0 + 1.5 \sqrt{I}} \]
| acMolality | Output vector containing the molality based activity coefficients. length: m_kk. |
Reimplemented in IdealMolalSoln, and DebyeHuckel.
Definition at line 210 of file MolalityVPSSTP.cpp.
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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.
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overridevirtual |
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.
Reimplemented from Phase.
Definition at line 343 of file MolalityVPSSTP.cpp.
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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.
| 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.
| t | Temperature (K) |
| p | Pressure (Pa) |
| molalities | Input vector of molalities of the solutes. Length: m_kk. |
Definition at line 234 of file MolalityVPSSTP.cpp.
| void setState_TPM | ( | double | t, |
| double | p, | ||
| const Composition & | m | ||
| ) |
Set the temperature (K), pressure (Pa), and molalities.
| t | Temperature (K) |
| p | Pressure (Pa) |
| m | Composition containing the molalities |
Definition at line 240 of file MolalityVPSSTP.cpp.
| void setState_TPM | ( | double | t, |
| double | p, | ||
| const string & | m | ||
| ) |
Set the temperature (K), pressure (Pa), and molalities.
| t | Temperature (K) |
| p | Pressure (Pa) |
| m | String which gets translated into a composition map for the molalities of the solutes. |
Definition at line 246 of file MolalityVPSSTP.cpp.
|
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 temperatureP 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.
|
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.
| ld | Number of rows in the matrix |
| dlnActCoeffdlnN | Output vector of derivatives of the log Activity Coefficients. length = m_kk * m_kk |
Reimplemented from ThermoPhase.
Definition at line 535 of file MolalityVPSSTP.h.
|
overridevirtual |
returns a summary of the state of the phase as a string
| show_thermo | If true, extra information is printed out about the thermodynamic state of the system. |
| threshold | Show information about species with mole fractions greater than threshold. |
Reimplemented from ThermoPhase.
Definition at line 357 of file MolalityVPSSTP.cpp.
|
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.
| acMolality | Output vector containing the molality based activity coefficients. length: m_kk. |
Reimplemented in HMWSoln.
Definition at line 277 of file MolalityVPSSTP.cpp.
|
protectedvirtual |
Apply the current phScale to a set of activity Coefficients or activities.
See the Eq3/6 Manual for a thorough discussion.
| acMolality | input/Output vector containing the molality based activity coefficients. length: m_kk. |
Reimplemented in HMWSoln.
Definition at line 282 of file MolalityVPSSTP.cpp.
|
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.
|
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.
|
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.
|
protected |
Molecular weight of the Solvent.
Definition at line 598 of file MolalityVPSSTP.h.
|
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.
|
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.
|
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.
1.9.1