Cantera 2.6.0

Public Member Functions | Protected Member Functions | Protected Attributes | Private Member Functions | List of all members
MolalityVPSSTP Class Reference

`#include <MolalityVPSSTP.h>`

Inheritance diagram for MolalityVPSSTP:
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Collaboration diagram for MolalityVPSSTP:
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## Public Member Functions
| MolalityVPSSTP ()
| Default Constructor. More...
virtual void | setStateFromXML (const XML_Node &state)
| Set equation of state parameter values from XML entries. More...
void | setState_TPM (doublereal t, doublereal p, const doublereal *const molalities)
| Set the temperature (K), pressure (Pa), and molalities (gmol kg-1) of the solutes. More...
void | setState_TPM (doublereal t, doublereal p, const compositionMap &m)
| Set the temperature (K), pressure (Pa), and molalities. More...
void | setState_TPM (doublereal t, doublereal p, const std::string &m)
| Set the temperature (K), pressure (Pa), and molalities. More...
virtual void | setState (const AnyMap &state)
| Set the state using an AnyMap containing any combination of properties supported by the thermodynamic model. More...
virtual void | getdlnActCoeffdlnN (const size_t ld, doublereal *const dlnActCoeffdlnN)
| Get the array of derivatives of the log activity coefficients with respect to the log of the species mole numbers. More...
virtual std::string | report (bool show_thermo=true, doublereal threshold=1e-14) const
| returns a summary of the state of the phase as a string More...
Utilities
virtual std::string | phaseOfMatter () const
| 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 (doublereal xmolSolventMIN)
| Sets the minimum mole fraction in the molality formulation. More...
doublereal | 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 (doublereal *const molal) const
| This function will return the molalities of the species. More...
void | setMolalities (const doublereal *const molal)
| Set the molalities of the solutes in a phase. More...
void | setMolalitiesByName (const compositionMap &xMap)
| Set the molalities of a phase. More...
void | setMolalitiesByName (const std::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 \[ \mu_k = \mu_k^0(T) + \hat R T \log a_k. \] The quantity \(\mu_k^0(T,P)\) is the chemical potential at unit activity, which depends only on temperature and pressure.
int | activityConvention () const
| We set the convention to molality here. More...
virtual void | getActivityConcentrations (doublereal *c) const
| This method returns an array of generalized concentrations. More...
virtual doublereal | standardConcentration (size_t k=0) const
| Return the standard concentration for the kth species. More...
virtual void | getActivities (doublereal *ac) const
| 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...
virtual void | getActivityCoefficients (doublereal *ac) const
| Get the array of non-dimensional activity coefficients at the current solution temperature, pressure, and solution concentration. More...
virtual void | getMolalityActivityCoefficients (doublereal *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().
virtual bool | addSpecies (shared_ptr< Species > spec)
virtual void | initThermo ()
Public Member Functions inherited from VPStandardStateTP
virtual void | setTemperature (const doublereal temp)
| Set the temperature of the phase. More...
virtual void | setPressure (doublereal p)
| Set the internally stored pressure (Pa) at constant temperature and composition. More...
virtual void | setState_TP (doublereal T, doublereal pres)
| Set the temperature and pressure at the same time. More...
virtual doublereal | pressure () const
| 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...
virtual double | minTemp (size_t k=npos) const
| Minimum temperature for which the thermodynamic data for the species or phase are valid. More...
virtual double | maxTemp (size_t k=npos) const
| 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...
virtual | ~VPStandardStateTP ()
virtual bool | isCompressible () const
| Return whether phase represents a compressible substance. More...
virtual int | standardStateConvention () const
| 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...
virtual void | getdlnActCoeffdlnN_diag (doublereal *dlnActCoeffdlnN_diag) const
| Get the array of log species mole number derivatives of the log activity coefficients. More...
virtual void | getChemPotentials_RT (doublereal *mu) const
| Get the array of non-dimensional species chemical potentials. More...
virtual void | getStandardChemPotentials (doublereal *mu) const
| 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...
virtual void | getEnthalpy_RT (doublereal *hrt) const
| Get the nondimensional Enthalpy functions for the species at their standard states at the current T and P of the solution. More...
virtual void | getEntropy_R (doublereal *sr) const
| Get the array of nondimensional Entropy functions for the standard state species at the current T and P of the solution. More...
virtual void | getGibbs_RT (doublereal *grt) const
| Get the nondimensional Gibbs functions for the species in their standard states at the current T and P of the solution. More...
virtual void | getPureGibbs (doublereal *gpure) const
| Get the Gibbs functions for the standard state of the species at the current T and P of the solution. More...
virtual void | getIntEnergy_RT (doublereal *urt) const
| Returns the vector of nondimensional Internal Energies of the standard state species at the current T and P of the solution. More...
virtual void | getCp_R (doublereal *cpr) const
| Get the nondimensional Heat Capacities at constant pressure for the species standard states at the current T and P of the solution. More...
virtual void | getStandardVolumes (doublereal *vol) const
| Get the molar volumes of the species standard states at the current T and P of the solution. More...
virtual const vector_fp & | getStandardVolumes () const
virtual void | getSpeciesParameters (const std::string &name, AnyMap &speciesNode) const
| Get phase-specific parameters of a Species object such that an identical one could be reconstructed and added to this phase. More...
void | installPDSS (size_t k, std::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...
virtual void | getEnthalpy_RT_ref (doublereal *hrt) const
virtual void | getGibbs_RT_ref (doublereal *grt) const
| 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...
virtual void | getGibbs_ref (doublereal *g) const
| 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...
virtual void | getEntropy_R_ref (doublereal *er) const
| 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...
virtual void | getCp_R_ref (doublereal *cprt) const
| 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...
virtual void | getStandardVolumes_ref (doublereal *vol) const
| 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 ()
| Constructor. More...
doublereal | 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...
virtual std::string | type () const
| String indicating the thermodynamic model implemented. More...
virtual bool | isIdeal () const
| Boolean indicating whether phase is ideal. More...
virtual doublereal | refPressure () const
| Returns the reference pressure in Pa. More...
doublereal | 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 doublereal 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 doublereal | enthalpy_mole () const
| Molar enthalpy. Units: J/kmol. More...
virtual doublereal | intEnergy_mole () const
| Molar internal energy. Units: J/kmol. More...
virtual doublereal | entropy_mole () const
| Molar entropy. Units: J/kmol/K. More...
virtual doublereal | gibbs_mole () const
| Molar Gibbs function. Units: J/kmol. More...
virtual doublereal | cp_mole () const
| Molar heat capacity at constant pressure. Units: J/kmol/K. More...
virtual doublereal | cv_mole () const
| Molar heat capacity at constant volume. Units: J/kmol/K. More...
virtual doublereal | isothermalCompressibility () const
| Returns the isothermal compressibility. Units: 1/Pa. More...
virtual doublereal | thermalExpansionCoeff () const
| Return the volumetric thermal expansion coefficient. Units: 1/K. More...
void | setElectricPotential (doublereal v)
| Set the electric potential of this phase (V). More...
doublereal | 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 doublereal | logStandardConc (size_t k=0) const
| Natural logarithm of the standard concentration of the kth species. More...
virtual void | getLnActivityCoefficients (doublereal *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 (doublereal *mu) const
| Get the species chemical potentials. Units: J/kmol. More...
void | getElectrochemPotentials (doublereal *mu) const
| Get the species electrochemical potentials. More...
virtual void | getPartialMolarEnthalpies (doublereal *hbar) const
| Returns an array of partial molar enthalpies for the species in the mixture. More...
virtual void | getPartialMolarEntropies (doublereal *sbar) const
| Returns an array of partial molar entropies of the species in the solution. More...
virtual void | getPartialMolarIntEnergies (doublereal *ubar) const
| Return an array of partial molar internal energies for the species in the mixture. More...
virtual void | getPartialMolarCp (doublereal *cpbar) const
| Return an array of partial molar heat capacities for the species in the mixture. More...
virtual void | getPartialMolarVolumes (doublereal *vbar) const
| Return an array of partial molar volumes for the species in the mixture. More...
virtual void | getIntEnergy_RT_ref (doublereal *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...
doublereal | enthalpy_mass () const
| Specific enthalpy. Units: J/kg. More...
doublereal | intEnergy_mass () const
| Specific internal energy. Units: J/kg. More...
doublereal | entropy_mass () const
| Specific entropy. Units: J/kg/K. More...
doublereal | gibbs_mass () const
| Specific Gibbs function. Units: J/kg. More...
doublereal | cp_mass () const
| Specific heat at constant pressure. Units: J/kg/K. More...
doublereal | cv_mass () const
| Specific heat at constant volume. Units: J/kg/K. More...
virtual void | setState_TPX (doublereal t, doublereal p, const doublereal *x)
| Set the temperature (K), pressure (Pa), and mole fractions. More...
virtual void | setState_TPX (doublereal t, doublereal p, const compositionMap &x)
| Set the temperature (K), pressure (Pa), and mole fractions. More...
virtual void | setState_TPX (doublereal t, doublereal p, const std::string &x)
| Set the temperature (K), pressure (Pa), and mole fractions. More...
virtual void | setState_TPY (doublereal t, doublereal p, const doublereal *y)
| Set the internally stored temperature (K), pressure (Pa), and mass fractions of the phase. More...
virtual void | setState_TPY (doublereal t, doublereal p, const compositionMap &y)
| Set the internally stored temperature (K), pressure (Pa), and mass fractions of the phase. More...
virtual void | setState_TPY (doublereal t, doublereal p, const std::string &y)
| Set the internally stored temperature (K), pressure (Pa), and mass fractions of the phase. More...
virtual void | setState_PX (doublereal p, doublereal *x)
| Set the pressure (Pa) and mole fractions. More...
virtual void | setState_PY (doublereal p, doublereal *y)
| Set the internally stored pressure (Pa) and mass fractions. 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_RP (doublereal rho, doublereal p)
| Set the density (kg/m**3) and pressure (Pa) at constant composition. More...
virtual void | setState_RPX (doublereal rho, doublereal p, const doublereal *x)
| Set the density (kg/m**3), pressure (Pa) and mole fractions. More...
virtual void | setState_RPX (doublereal rho, doublereal p, const compositionMap &x)
| Set the density (kg/m**3), pressure (Pa) and mole fractions. More...
virtual void | setState_RPX (doublereal rho, doublereal p, const std::string &x)
| Set the density (kg/m**3), pressure (Pa) and mole fractions. More...
virtual void | setState_RPY (doublereal rho, doublereal p, const doublereal *y)
| Set the density (kg/m**3), pressure (Pa) and mass fractions. More...
virtual void | setState_RPY (doublereal rho, doublereal p, const compositionMap &y)
| Set the density (kg/m**3), pressure (Pa) and mass fractions. More...
virtual void | setState_RPY (doublereal rho, doublereal p, const std::string &y)
| Set the density (kg/m**3), pressure (Pa) and mass fractions. 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 std::string &fuelComp, const std::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 compositionMap &fuelComp, const compositionMap &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 std::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 std::string &fuelComp, const std::string &oxComp, ThermoBasis basis=ThermoBasis::molar, const std::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 compositionMap &fuelComp, const compositionMap &oxComp, ThermoBasis basis=ThermoBasis::molar, const std::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 std::string &fuelComp, const std::string &oxComp, ThermoBasis basis=ThermoBasis::molar)
| Set the mixture composition according to the equivalence ratio. More...
void | setEquivalenceRatio (double phi, const compositionMap &fuelComp, const compositionMap &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 std::string &fuelComp, const std::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 compositionMap &fuelComp, const compositionMap &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 std::string &fuelComp, const std::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 compositionMap &fuelComp, const compositionMap &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 std::string &XY, const std::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 doublereal *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 doublereal | critTemperature () const
| Critical temperature (K). More...
virtual doublereal | critPressure () const
| Critical pressure (Pa). More...
virtual doublereal | critVolume () const
| Critical volume (m3/kmol). More...
virtual doublereal | critCompressibility () const
| Critical compressibility (unitless). More...
virtual doublereal | critDensity () const
| Critical density (kg/m3). More...
virtual doublereal | satTemperature (doublereal p) const
| Return the saturation temperature given the pressure. More...
virtual doublereal | satPressure (doublereal t)
| Return the saturation pressure given the temperature. More...
virtual doublereal | vaporFraction () const
| Return the fraction of vapor at the current conditions. More...
virtual void | setState_Tsat (doublereal t, doublereal x)
| Set the state to a saturated system at a particular temperature. More...
virtual void | setState_Psat (doublereal p, doublereal 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...
virtual void | modifySpecies (size_t k, shared_ptr< Species > spec)
| Modify the thermodynamic data associated with a species. More...
void | saveSpeciesData (const size_t k, const XML_Node *const data)
| Store a reference pointer to the XML tree containing the species data for this phase. More...
const std::vector< const XML_Node * > & | speciesData () const
| Return a pointer to the vector of XML nodes containing the species data for this phase. 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 std::string &inputFile, const std::string &id)
virtual void | initThermoXML (XML_Node &phaseNode, const std::string &id)
| Import and initialize a ThermoPhase object using an XML tree. More...
virtual void | setParameters (int n, doublereal *const c)
| Set the equation of state parameters. More...
virtual void | getParameters (int &n, doublereal *const c) const
| Get the equation of state parameters in a vector. 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 newPhase(AnyMap&) function. More...
const AnyMap & | input () const
| Access input data associated with the phase description. More...
AnyMap & | input ()
virtual void | setParametersFromXML (const XML_Node &eosdata)
| Set equation of state parameter values from XML entries. More...
virtual void | getdlnActCoeffds (const doublereal dTds, const doublereal *const dXds, doublereal *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 (doublereal *dlnActCoeffdlnX_diag) const
| Get the array of ln mole fraction derivatives of the log activity coefficients - diagonal component only. More...
virtual void | getdlnActCoeffdlnN_numderiv (const size_t ld, doublereal *const dlnActCoeffdlnN)
virtual void | reportCSV (std::ofstream &csvFile) const
| returns a summary of the state of the phase to a comma separated file. More...
Public Member Functions inherited from Phase
| Phase ()
| Default constructor. More...
| Phase (const Phase &)=delete
Phase & | operator= (const Phase &)=delete
XML_Node & | xml () const
| Returns a const reference to the XML_Node that describes the phase. More...
void | setXMLdata (XML_Node &xmlPhase)
| Stores the XML tree information for the current phase. More...
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 bool | isCompressible () const
| Return whether phase represents a compressible substance. More...
virtual std::map< std::string, size_t > | nativeState () const
| Return a map of properties defining the native state of a substance. More...
virtual std::vector< std::string > | fullStates () const
| Return a vector containing full states defining a phase. More...
virtual std::vector< std::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_fp &state) const
| Save the current internal state of the phase. More...
virtual void | saveState (size_t lenstate, doublereal *state) const
| Write to array 'state' the current internal state. More...
void | restoreState (const vector_fp &state)
| Restore a state saved on a previous call to saveState. More...
virtual void | restoreState (size_t lenstate, const doublereal *state)
| Restore the state of the phase from a previously saved state vector. More...
doublereal | molecularWeight (size_t k) const
| Molecular weight of species `k`. More...
void | getMolecularWeights (vector_fp &weights) const
| Copy the vector of molecular weights into vector weights. More...
void | getMolecularWeights (doublereal *weights) const
| Copy the vector of molecular weights into array weights. More...
const vector_fp & | molecularWeights () 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...
doublereal | elementalMassFraction (const size_t m) const
| Elemental mass fraction of element m. More...
doublereal | elementalMoleFraction (const size_t m) const
| Elemental mole fraction of element m. More...
const double * | moleFractdivMMW () const
| Returns a const pointer to the start of the moleFraction/MW array. More...
doublereal | 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...
doublereal | 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...
virtual void | invalidateCache ()
| Invalidate any cached values which are normally updated only when a change in state is detected. 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...
virtual void | setRoot (std::shared_ptr< Solution > root)
| Set root Solution holding all phase information. More...
vector_fp | getCompositionFromMap (const compositionMap &comp) const
| Converts a compositionMap 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...
std::string | name () const
| Return the name of the phase. More...
void | setName (const std::string &nm)
| Sets the string name for the phase. More...
std::string | elementName (size_t m) const
| Name of the element with index m. More...
size_t | elementIndex (const std::string &name) const
| Return the index of element named 'name'. More...
const std::vector< std::string > & | elementNames () const
| Return a read-only reference to the vector of element names. More...
doublereal | atomicWeight (size_t m) const
| Atomic weight of element m. More...
doublereal | 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_fp & | 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...
doublereal | nAtoms (size_t k, size_t m) const
| Number of atoms of element `m` in species `k`. More...
void | getAtoms (size_t k, double *atomArray) const
| Get a vector containing the atomic composition of species k. More...
size_t | speciesIndex (const std::string &name) const
| Returns the index of a species named 'name' within the Phase object. More...
std::string | speciesName (size_t k) const
| Name of the species with index k. More...
std::string | speciesSPName (int k) const
| Returns the expanded species name of a species, including the phase name This is guaranteed to be unique within a Cantera problem. More...
const std::vector< std::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 compositionMap &xMap)
| Set the species mole fractions by name. More...
void | setMoleFractionsByName (const std::string &x)
| Set the mole fractions of a group of species by name. More...
void | setMassFractionsByName (const compositionMap &yMap)
| Set the species mass fractions by name. More...
void | setMassFractionsByName (const std::string &x)
| Set the species mass fractions by name. More...
void | setState_TRX (doublereal t, doublereal dens, const doublereal *x)
| Set the internally stored temperature (K), density, and mole fractions. More...
void | setState_TRX (doublereal t, doublereal dens, const compositionMap &x)
| Set the internally stored temperature (K), density, and mole fractions. More...
void | setState_TRY (doublereal t, doublereal dens, const doublereal *y)
| Set the internally stored temperature (K), density, and mass fractions. More...
void | setState_TRY (doublereal t, doublereal dens, const compositionMap &y)
| Set the internally stored temperature (K), density, and mass fractions. More...
void | setState_TNX (doublereal t, doublereal n, const doublereal *x)
| Set the internally stored temperature (K), molar density (kmol/m^3), and mole fractions. More...
void | setState_TR (doublereal t, doublereal rho)
| Set the internally stored temperature (K) and density (kg/m^3) More...
void | setState_TX (doublereal t, doublereal *x)
| Set the internally stored temperature (K) and mole fractions. More...
void | setState_TY (doublereal t, doublereal *y)
| Set the internally stored temperature (K) and mass fractions. More...
void | setState_RX (doublereal rho, doublereal *x)
| Set the density (kg/m^3) and mole fractions. More...
void | setState_RY (doublereal rho, doublereal *y)
| Set the density (kg/m^3) and mass fractions. More...
compositionMap | 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 std::string &name) const
| Return the mole fraction of a single species. More...
compositionMap | 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 std::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...
void | getConcentrations (double *const c) const
| Get the species concentrations (kmol/m^3). More...
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...
doublereal | temperature () const
| Temperature (K). More...
virtual double | electronTemperature () const
| Electron Temperature (K) More...
virtual double | density () const
| Density (kg/m^3). More...
double | molarDensity () const
| Molar density (kmol/m^3). More...
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 | setMolarDensity (const double molarDensity)
| Set the internally stored molar density (kmol/m^3) of the phase. More...
virtual void | setElectronTemperature (double etemp)
| Set the internally stored electron temperature of the phase (K). More...
doublereal | mean_X (const doublereal *const Q) const
| Evaluate the mole-fraction-weighted mean of an array Q. More...
doublereal | mean_X (const vector_fp &Q) const
| Evaluate the mole-fraction-weighted mean of an array Q. More...
doublereal | meanMolecularWeight () const
| The mean molecular weight. Units: (kg/kmol) More...
doublereal | sum_xlogx () const
| Evaluate \( \sum_k X_k \log X_k \). More...
size_t | addElement (const std::string &symbol, doublereal weight=-12345.0, int atomicNumber=0, doublereal entropy298=ENTROPY298_UNKNOWN, int elem_type=CT_ELEM_TYPE_ABSPOS)
| Add an element. More...
void | addSpeciesAlias (const std::string &name, const std::string &alias)
| Add a species alias (that is, a user-defined alternative species name). More...
virtual std::vector< std::string > | findIsomers (const compositionMap &compMap) const
| Return a vector with isomers names matching a given composition map. More...
virtual std::vector< std::string > | findIsomers (const std::string &comp) const
| Return a vector with isomers names matching a given composition string. More...
shared_ptr< Species > | species (const std::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 | getCsvReportData (std::vector< std::string > &names, std::vector< vector_fp > &data) const
| Fills `names` and `data` with the column names and species thermo properties to be included in the output of the reportCSV method. More...
virtual void | getUnscaledMolalityActivityCoefficients (doublereal *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 (doublereal *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...
virtual void | invalidateCache ()
| Invalidate any cached values which are normally updated only when a change in state is detected. More...
const vector_fp & | 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 newPhase(AnyMap&) function. More...
virtual void | getCsvReportData (std::vector< std::string > &names, std::vector< vector_fp > &data) const
| Fills `names` and `data` with the column names and species thermo properties to be included in the output of the reportCSV method. More...
Protected Member Functions inherited from Phase
void | assertCompressible (const std::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
| Scaling to be used for output of single-ion species activity coefficients. More...
size_t | m_indexCLM
| Index of the phScale species. More...
doublereal | m_weightSolvent
| Molecular weight of the Solvent. More...
doublereal | m_xmolSolventMIN
doublereal | m_Mnaught
| This is the multiplication factor that goes inside log expressions involving the molalities of species. More...
vector_fp | m_molalities
| Current value of the molalities of the species in the phase. More...
Protected Attributes inherited from VPStandardStateTP
doublereal | m_Pcurrent
| Current value of the pressure - state variable. More...
double | m_minTemp
| The minimum temperature at which data for all species is valid. More...
double | m_maxTemp
| The maximum temperature at which data for all species is valid. More...
doublereal | m_Tlast_ss
| The last temperature at which the standard state thermodynamic properties were calculated at. More...
doublereal | m_Plast_ss
| The last pressure at which the Standard State thermodynamic properties were calculated at. More...
std::vector< std::unique_ptr< PDSS > > | m_PDSS_storage
| Storage for the PDSS objects for the species. More...
vector_fp | m_h0_RT
| Vector containing the species reference enthalpies at T = m_tlast and P = p_ref. More...
vector_fp | m_cp0_R
| Vector containing the species reference constant pressure heat capacities at T = m_tlast and P = p_ref. More...
vector_fp | m_g0_RT
| Vector containing the species reference Gibbs functions at T = m_tlast and P = p_ref. More...
vector_fp | m_s0_R
| Vector containing the species reference entropies at T = m_tlast and P = p_ref. More...
vector_fp | m_V0
| Vector containing the species reference molar volumes. More...
vector_fp | m_hss_RT
| Vector containing the species Standard State enthalpies at T = m_tlast and P = m_plast. More...
vector_fp | m_cpss_R
| Vector containing the species Standard State constant pressure heat capacities at T = m_tlast and P = m_plast. More...
vector_fp | m_gss_RT
| Vector containing the species Standard State Gibbs functions at T = m_tlast and P = m_plast. More...
vector_fp | m_sss_R
| Vector containing the species Standard State entropies at T = m_tlast and P = m_plast. More...
vector_fp | 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...
std::vector< const XML_Node * > | m_speciesData
| Vector of pointers to the species databases. More...
doublereal | m_phi
| Stored value of the electric potential for this phase. Units are Volts. More...
bool | m_chargeNeutralityNecessary
| Boolean indicating whether a charge neutrality condition is a necessity. More...
int | m_ssConvention
| Contains the standard state convention. More...
doublereal | m_tlast
| 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
| Number of species in the phase. More...
size_t | m_ndim
| Dimensionality of the phase. More...
vector_fp | m_speciesComp
| Atomic composition of the species. More...
vector_fp | m_speciesCharge
| Vector of species charges. length m_kk. More...
std::map< std::string, shared_ptr< Species > > | m_species
UndefElement::behavior | m_undefinedElementBehavior
| Flag determining behavior when adding species with an undefined element. More...
bool | m_caseSensitiveSpecies
| Flag determining whether case sensitive species names are enforced. More...

## Private Member Functions
virtual size_t | findCLMIndex () const
| Returns the index of the Cl- species. More...

## 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 181 of file MolalityVPSSTP.h.

## Constructor & Destructor Documentation

## ◆ MolalityVPSSTP()

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 24 of file MolalityVPSSTP.cpp.

References ThermoPhase::m_chargeNeutralityNecessary.

## Member Function Documentation

## ◆ phaseOfMatter()

virtual std::string phaseOfMatter | ( |  | ) | const
| inline virtual

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 201 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

  pHscaleType | Integer representing the pHscale

Definition at line 39 of file MolalityVPSSTP.cpp.

References MolalityVPSSTP::m_pHScalingType, Cantera::PHSCALE_NBS, and Cantera::PHSCALE_PITZER.

## ◆ 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 48 of file MolalityVPSSTP.cpp.

References MolalityVPSSTP::m_pHScalingType.

## ◆ setMoleFSolventMin()

void setMoleFSolventMin | ( | doublereal | 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

  xmolSolventMIN | Input double containing the minimum mole fraction

Definition at line 53 of file MolalityVPSSTP.cpp.

References MolalityVPSSTP::m_xmolSolventMIN.

Referenced by IdealMolalSoln::initThermo().

## ◆ moleFSolventMin()

doublereal moleFSolventMin | ( |  | ) | const

Returns the minimum mole fraction in the molality formulation.

Definition at line 63 of file MolalityVPSSTP.cpp.

References MolalityVPSSTP::m_xmolSolventMIN.

## ◆ 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 68 of file MolalityVPSSTP.cpp.

References Phase::getMoleFractions(), Phase::m_kk, MolalityVPSSTP::m_Mnaught, MolalityVPSSTP::m_molalities, and MolalityVPSSTP::m_xmolSolventMIN.

Referenced by DebyeHuckel::_lnactivityWaterHelgesonFixedForm(), IdealMolalSoln::getActivities(), IdealMolalSoln::getChemPotentials(), MolalityVPSSTP::getMolalities(), IdealMolalSoln::getPartialMolarEntropies(), HMWSoln::printCoeffs(), DebyeHuckel::s_update_lnMolalityActCoeff(), HMWSoln::s_updateIMS_lnMolalityActCoeff(), IdealMolalSoln::s_updateIMS_lnMolalityActCoeff(), MolalityVPSSTP::setMolalities(), and MolalityVPSSTP::setMolalitiesByName().

## ◆ getMolalities()

void getMolalities | ( | doublereal *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

  molal | Output vector of molalities. Length: m_kk.

Definition at line 78 of file MolalityVPSSTP.cpp.

References MolalityVPSSTP::calcMolalities(), Phase::m_kk, and MolalityVPSSTP::m_molalities.

Referenced by MolalityVPSSTP::getCsvReportData(), and vcs_MultiPhaseEquil::reportCSV().

## ◆ setMolalities()

void setMolalities | ( | const doublereal *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

  molal | Input vector of molalities. Length: m_kk.

Definition at line 86 of file MolalityVPSSTP.cpp.

References MolalityVPSSTP::calcMolalities(), Phase::m_kk, MolalityVPSSTP::m_Mnaught, MolalityVPSSTP::m_molalities, and Phase::setMoleFractions().

Referenced by MolalityVPSSTP::setState_TPM().

## ◆ setMolalitiesByName() [1/2]

void setMolalitiesByName | ( | const compositionMap & | 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

  xMap | Composition Map containing the molalities.

Definition at line 113 of file MolalityVPSSTP.cpp.

References MolalityVPSSTP::calcMolalities(), Phase::charge(), Phase::getMoleFractions(), Cantera::getValue(), Phase::m_kk, MolalityVPSSTP::m_Mnaught, MolalityVPSSTP::m_xmolSolventMIN, Cantera::npos, Phase::setMoleFractions(), and Phase::speciesName().

Referenced by MolalityVPSSTP::setMolalitiesByName(), MolalityVPSSTP::setState(), MolalityVPSSTP::setState_TPM(), and MolalityVPSSTP::setStateFromXML().

## ◆ setMolalitiesByName() [2/2]

void setMolalitiesByName | ( | const std::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

  name | String containing the information for a composition map.

Definition at line 181 of file MolalityVPSSTP.cpp.

References Cantera::parseCompString(), MolalityVPSSTP::setMolalitiesByName(), and Phase::speciesNames().

## ◆ activityConvention()

int activityConvention | ( |  | ) | const
| virtual

We set the convention to molality here.

Reimplemented from ThermoPhase.

Definition at line 189 of file MolalityVPSSTP.cpp.

References Cantera::cAC_CONVENTION_MOLALITY.

## ◆ getActivityConcentrations()

void getActivityConcentrations | ( | doublereal * | c | ) | const
| virtual

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

  c | Output array of generalized concentrations. The units depend upon the implementation of the reaction rate expressions within the phase.

Reimplemented from ThermoPhase.

Reimplemented in DebyeHuckel, HMWSoln, and IdealMolalSoln.

Definition at line 194 of file MolalityVPSSTP.cpp.

## ◆ standardConcentration()

doublereal standardConcentration | ( | size_t | k = `0` | ) | const
| virtual

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

  k | Optional 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.

Reimplemented in DebyeHuckel, HMWSoln, and IdealMolalSoln.

Definition at line 199 of file MolalityVPSSTP.cpp.

## ◆ getActivities()

void getActivities | ( | doublereal * | ac | ) | const
| virtual

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

  ac | Output vector of molality-based activities. Length: m_kk.

Reimplemented from ThermoPhase.

Reimplemented in DebyeHuckel, HMWSoln, and IdealMolalSoln.

Definition at line 204 of file MolalityVPSSTP.cpp.

Referenced by MolalityVPSSTP::getCsvReportData(), and MolalityVPSSTP::osmoticCoefficient().

## ◆ getActivityCoefficients()

void getActivityCoefficients | ( | doublereal * | ac | ) | const
| virtual

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 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

  ac | Output vector containing the mole-fraction based activity coefficients. length: m_kk.

Reimplemented from ThermoPhase.

Definition at line 209 of file MolalityVPSSTP.cpp.

References MolalityVPSSTP::getMolalityActivityCoefficients(), Phase::m_kk, MolalityVPSSTP::m_xmolSolventMIN, and Phase::moleFraction().

## ◆ getMolalityActivityCoefficients()

void getMolalityActivityCoefficients | ( | doublereal * | 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 for a thorough discussion. This class 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

  acMolality | Output vector containing the molality based activity coefficients. length: m_kk.

Reimplemented in DebyeHuckel, and IdealMolalSoln.

Definition at line 218 of file MolalityVPSSTP.cpp.

References MolalityVPSSTP::applyphScale(), and MolalityVPSSTP::getUnscaledMolalityActivityCoefficients().

Referenced by MolalityVPSSTP::getActivityCoefficients(), and MolalityVPSSTP::getCsvReportData().

## ◆ osmoticCoefficient()

doublereal 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 224 of file MolalityVPSSTP.cpp.

References MolalityVPSSTP::getActivities(), Phase::m_kk, MolalityVPSSTP::m_Mnaught, and MolalityVPSSTP::m_molalities.

## ◆ setStateFromXML()

void setStateFromXML | ( | const XML_Node & | state | ) |
| virtual

Set equation of state parameter values from XML entries.

This method is called by function importPhase() when processing a phase definition in an input file. It should be overloaded in subclasses to set any parameters that are specific to that particular phase model.

The MolalityVPSSTP object defines a new method for setting the concentrations of a phase. The new method is defined by a block called "soluteMolalities". If this block is found, the concentrations within that phase are set to the "name":"molalities pairs found within that XML block. The solvent concentration is then set to everything else. The function first calls the overloaded function, VPStandardStateTP::setStateFromXML(), to pick up the parent class behavior. usage: Overloaded functions should call this function before carrying out their own behavior. @param state An XML_Node object corresponding to the "state" entry for this phase in the input file.

Deprecated:
  The XML input format is deprecated and will be removed in Cantera 3.0.

Reimplemented from ThermoPhase.

Definition at line 242 of file MolalityVPSSTP.cpp.

References Cantera::getChildValue(), Cantera::getFloat(), XML_Node::hasChild(), MolalityVPSSTP::setMolalitiesByName(), VPStandardStateTP::setPressure(), and ThermoPhase::setStateFromXML().

## ◆ addSpecies()

bool addSpecies | ( | shared_ptr< Species > | spec | ) |
| virtual

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().

Reimplemented from VPStandardStateTP.

Reimplemented in DebyeHuckel, and IdealMolalSoln.

Definition at line 365 of file MolalityVPSSTP.cpp.

References VPStandardStateTP::addSpecies(), Phase::m_kk, MolalityVPSSTP::m_Mnaught, MolalityVPSSTP::m_molalities, MolalityVPSSTP::m_weightSolvent, and Phase::molecularWeight().

Referenced by DebyeHuckel::addSpecies(), and IdealMolalSoln::addSpecies().

## ◆ initThermo()

void initThermo | ( |  | ) |
| virtual

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().

Reimplemented from VPStandardStateTP.

Reimplemented in DebyeHuckel, HMWSoln, and IdealMolalSoln.

Definition at line 291 of file MolalityVPSSTP.cpp.

References MolalityVPSSTP::findCLMIndex(), VPStandardStateTP::initThermo(), and MolalityVPSSTP::m_indexCLM.

Referenced by DebyeHuckel::initThermo(), HMWSoln::initThermo(), and IdealMolalSoln::initThermo().

## ◆ setState_TPM() [1/3]

void setState_TPM | ( | doublereal | t,
|  | doublereal | p,
|  | const doublereal *const | molalities
| ) |  |

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

Parameters

  t | Temperature (K)
  p | Pressure (Pa)
  molalities | Input vector of molalities of the solutes. Length: m_kk.

Definition at line 255 of file MolalityVPSSTP.cpp.

References MolalityVPSSTP::setMolalities(), and VPStandardStateTP::setState_TP().

## ◆ setState_TPM() [2/3]

void setState_TPM | ( | doublereal | t,
|  | doublereal | p,
|  | const compositionMap & | m
| ) |  |

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

Parameters

  t | Temperature (K)
  p | Pressure (Pa)
  m | compositionMap containing the molalities

Definition at line 262 of file MolalityVPSSTP.cpp.

References MolalityVPSSTP::setMolalitiesByName(), and VPStandardStateTP::setState_TP().

## ◆ setState_TPM() [3/3]

void setState_TPM | ( | doublereal | t,
|  | doublereal | p,
|  | const std::string & | m
| ) |  |

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

Parameters

  t | Temperature (K)
  p | Pressure (Pa)
  m | String which gets translated into a composition map for the molalities of the solutes.

Definition at line 268 of file MolalityVPSSTP.cpp.

References MolalityVPSSTP::setMolalitiesByName(), and VPStandardStateTP::setState_TP().

## ◆ setState()

void setState | ( | const AnyMap & | state | ) |
| virtual

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 274 of file MolalityVPSSTP.cpp.

References AnyValue::asMap(), AnyValue::asString(), AnyMap::hasKey(), AnyValue::is(), MolalityVPSSTP::setMolalitiesByName(), and ThermoPhase::setState().

## ◆ getdlnActCoeffdlnN()

virtual void getdlnActCoeffdlnN | ( | const size_t | ld,
|  | doublereal *const | dlnActCoeffdlnN
| ) |  |
| inline virtual

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.

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

Parameters

  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 519 of file MolalityVPSSTP.h.

## ◆ report()

std::string report | ( | bool | show_thermo = `true`,
|  | doublereal | threshold = `1e-14`
| ) |  | const
| virtual

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

Parameters

  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 379 of file MolalityVPSSTP.cpp.

References Phase::name().

## ◆ getCsvReportData()

void getCsvReportData | ( | std::vector< std::string > & | names,
|  | std::vector< vector_fp > & | data
| ) |  | const
| protected virtual

Fills `names` and `data` with the column names and species thermo properties to be included in the output of the reportCSV method.

Reimplemented from ThermoPhase.

Definition at line 487 of file MolalityVPSSTP.cpp.

References MolalityVPSSTP::getActivities(), ThermoPhase::getChemPotentials(), MolalityVPSSTP::getMolalities(), MolalityVPSSTP::getMolalityActivityCoefficients(), Phase::getMoleFractions(), ThermoPhase::getPartialMolarCp(), ThermoPhase::getPartialMolarEnthalpies(), ThermoPhase::getPartialMolarEntropies(), ThermoPhase::getPartialMolarIntEnergies(), ThermoPhase::getPartialMolarVolumes(), VPStandardStateTP::getStandardChemPotentials(), and Phase::nSpecies().

## ◆ getUnscaledMolalityActivityCoefficients()

void getUnscaledMolalityActivityCoefficients | ( | doublereal * | acMolality | ) | const
| protected virtual

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

See Denbigh p. 278 for a thorough discussion. This class 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

  acMolality | Output vector containing the molality based activity coefficients. length: m_kk.

Reimplemented in HMWSoln.

Definition at line 299 of file MolalityVPSSTP.cpp.

Referenced by MolalityVPSSTP::getMolalityActivityCoefficients().

## ◆ applyphScale()

void applyphScale | ( | doublereal * | acMolality | ) | const
| protected virtual

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

See the Eq3/6 Manual for a thorough discussion.

Parameters

  acMolality | input/Output vector containing the molality based activity coefficients. length: m_kk.

Reimplemented in HMWSoln.

Definition at line 304 of file MolalityVPSSTP.cpp.

Referenced by MolalityVPSSTP::getMolalityActivityCoefficients().

## ◆ findCLMIndex()

size_t findCLMIndex | ( |  | ) | const
| private virtual

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 309 of file MolalityVPSSTP.cpp.

References Phase::elementName(), Phase::m_kk, Phase::nAtoms(), Phase::nElements(), Cantera::npos, and Phase::speciesName().

Referenced by MolalityVPSSTP::initThermo().

## Member Data Documentation

## ◆ m_pHScalingType

int m_pHScalingType
| 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 576 of file MolalityVPSSTP.h.

Referenced by HMWSoln::applyphScale(), MolalityVPSSTP::pHScale(), HMWSoln::s_updateScaling_pHScaling(), HMWSoln::s_updateScaling_pHScaling_dP(), HMWSoln::s_updateScaling_pHScaling_dT(), HMWSoln::s_updateScaling_pHScaling_dT2(), and MolalityVPSSTP::setpHScale().

## ◆ m_indexCLM

size_t m_indexCLM
| 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 583 of file MolalityVPSSTP.h.

Referenced by HMWSoln::applyphScale(), MolalityVPSSTP::initThermo(), HMWSoln::s_updateScaling_pHScaling(), HMWSoln::s_updateScaling_pHScaling_dP(), HMWSoln::s_updateScaling_pHScaling_dT(), and HMWSoln::s_updateScaling_pHScaling_dT2().

## ◆ m_weightSolvent

doublereal m_weightSolvent
| protected

Molecular weight of the Solvent.

Definition at line 586 of file MolalityVPSSTP.h.

Referenced by MolalityVPSSTP::addSpecies(), HMWSoln::s_updatePitzer_d2lnMolalityActCoeff_dT2(), HMWSoln::s_updatePitzer_dlnMolalityActCoeff_dP(), and HMWSoln::s_updatePitzer_dlnMolalityActCoeff_dT().

## ◆ m_xmolSolventMIN

doublereal m_xmolSolventMIN
| 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 595 of file MolalityVPSSTP.h.

Referenced by MolalityVPSSTP::calcMolalities(), IdealMolalSoln::getActivities(), MolalityVPSSTP::getActivityCoefficients(), IdealMolalSoln::getMolalityActivityCoefficients(), MolalityVPSSTP::moleFSolventMin(), HMWSoln::s_updateIMS_lnMolalityActCoeff(), IdealMolalSoln::s_updateIMS_lnMolalityActCoeff(), MolalityVPSSTP::setMolalitiesByName(), and MolalityVPSSTP::setMoleFSolventMin().

## ◆ m_Mnaught

doublereal m_Mnaught
| 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 600 of file MolalityVPSSTP.h.

Referenced by DebyeHuckel::_lnactivityWaterHelgesonFixedForm(), MolalityVPSSTP::addSpecies(), MolalityVPSSTP::calcMolalities(), HMWSoln::calcMolalitiesCropped(), MolalityVPSSTP::osmoticCoefficient(), MolalityVPSSTP::setMolalities(), MolalityVPSSTP::setMolalitiesByName(), and HMWSoln::standardConcentration().

## ◆ m_molalities

vector_fp m_molalities
| mutable protected

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 604 of file MolalityVPSSTP.h.

Referenced by DebyeHuckel::_lnactivityWaterHelgesonFixedForm(), MolalityVPSSTP::addSpecies(), MolalityVPSSTP::calcMolalities(), HMWSoln::calcMolalitiesCropped(), DebyeHuckel::getActivities(), HMWSoln::getActivities(), IdealMolalSoln::getActivities(), DebyeHuckel::getChemPotentials(), HMWSoln::getChemPotentials(), IdealMolalSoln::getChemPotentials(), MolalityVPSSTP::getMolalities(), DebyeHuckel::getPartialMolarEntropies(), HMWSoln::getPartialMolarEntropies(), IdealMolalSoln::getPartialMolarEntropies(), MolalityVPSSTP::osmoticCoefficient(), DebyeHuckel::s_update_lnMolalityActCoeff(), HMWSoln::s_updatePitzer_lnMolalityActCoeff(), and MolalityVPSSTP::setMolalities().

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

- MolalityVPSSTP.h
- MolalityVPSSTP.cpp