Cantera  3.1.0a1
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GibbsExcessVPSSTP Class Reference

GibbsExcessVPSSTP is a derived class of ThermoPhase that handles variable pressure standard state methods for calculating thermodynamic properties that are further based on expressing the Excess Gibbs free energy as a function of the mole fractions (or pseudo mole fractions) of constituents. More...

#include <GibbsExcessVPSSTP.h>

Inheritance diagram for GibbsExcessVPSSTP:
[legend]

Detailed Description

GibbsExcessVPSSTP is a derived class of ThermoPhase that handles variable pressure standard state methods for calculating thermodynamic properties that are further based on expressing the Excess Gibbs free energy as a function of the mole fractions (or pseudo mole fractions) of constituents.

This category is the workhorse for describing molten salts, solid-phase mixtures of semiconductors, and mixtures of miscible and semi-miscible compounds.

It includes

  • regular solutions
  • Margules expansions
  • NTRL equation
  • Wilson's equation
  • UNIQUAC equation of state.

This class adds additional functions onto the ThermoPhase interface that handles the calculation of the excess Gibbs free energy. 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. That default is used here.

All of the Excess Gibbs free energy formulations in this area employ symmetrical formulations.

Chemical potentials of species k, \( \mu_o \), has the following general format:

\[ \mu_k = \mu^o_k(T,P) + R T \ln( \gamma_k X_k ) \]

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

GibbsExcessVPSSTP contains an internal vector with the current mole fraction vector. That's one of its primary usages. In order to keep the mole fraction vector constant, all of the setState functions are redesigned at this layer.

Activity Concentrations: Relationship of ThermoPhase to Kinetics Expressions

As explained in a similar discussion in the ThermoPhase class, the actual units used in kinetics expressions must be specified in the ThermoPhase class for the corresponding species. These units vary with the field of study. Cantera uses the concept of activity concentrations to represent this. Activity concentrations are used directly in the expressions for kinetics. Standard concentrations are used as the multiplicative constant that takes the activity of a species and turns it into an activity concentration. Standard concentrations must not depend on the concentration of the species in the phase.

Here we set a standard for the specification of the standard concentrations for this class and all child classes underneath it. We specify here that the standard concentration is equal to 1 for all species. Therefore, the activities appear directly in kinetics expressions involving species in underlying GibbsExcessVPSSTP phases.

SetState Strategy

All setState functions that set the internal state of the ThermoPhase object are overloaded at this level, so that a current mole fraction vector is maintained within the object.

Definition at line 84 of file GibbsExcessVPSSTP.h.

Public Member Functions

bool addSpecies (shared_ptr< Species > spec) override
 Add a Species to this Phase.
 
Constructors
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.

Units standardConcentrationUnits () const override
 Returns the units of the "standard concentration" for this phase.
 
void getActivityConcentrations (double *c) const override
 This method returns an array of generalized concentrations.
 
double standardConcentration (size_t k=0) const override
 The standard concentration \( C^0_k \) used to normalize the generalized concentration.
 
double logStandardConc (size_t k=0) const override
 Natural logarithm of the standard concentration of the kth species.
 
void getActivities (double *ac) const override
 Get the array of non-dimensional activities (molality based for this class and classes that derive from it) at the current solution temperature, pressure, and solution concentration.
 
void getActivityCoefficients (double *ac) const override
 Get the array of non-dimensional molar-based activity coefficients at the current solution temperature, pressure, and solution concentration.
 
virtual void getdlnActCoeffdT (double *dlnActCoeffdT) const
 Get the array of temperature derivatives of the log activity coefficients.
 
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.
 
virtual void getdlnActCoeffdlnX (double *dlnActCoeffdlnX) const
 Get the array of log concentration-like derivatives of the log activity coefficients.
 
Partial Molar Properties of the Solution
void getPartialMolarVolumes (double *vbar) const override
 Return an array of partial molar volumes for the species in the mixture.
 
- Public Member Functions inherited from VPStandardStateTP
void setTemperature (const double temp) override
 Set the temperature of the phase.
 
void setPressure (double p) override
 Set the internally stored pressure (Pa) at constant temperature and composition.
 
void setState_TP (double T, double pres) override
 Set the temperature and pressure at the same time.
 
double pressure () const override
 Returns the current pressure of the phase.
 
virtual void updateStandardStateThermo () const
 Updates the standard state thermodynamic functions at the current T and P of the solution.
 
double minTemp (size_t k=npos) const override
 Minimum temperature for which the thermodynamic data for the species or phase are valid.
 
double maxTemp (size_t k=npos) const override
 Maximum temperature for which the thermodynamic data for the species are valid.
 
PDSSprovidePDSS (size_t k)
 
const PDSSprovidePDSS (size_t k) const
 
 VPStandardStateTP ()
 Constructor.
 
bool isCompressible () const override
 Return whether phase represents a compressible substance.
 
int standardStateConvention () const override
 This method returns the convention used in specification of the standard state, of which there are currently two, temperature based, and variable pressure based.
 
void getStandardChemPotentials (double *mu) const override
 Get the array of chemical potentials at unit activity for the species at their standard states at the current T and P of the solution.
 
void getEnthalpy_RT (double *hrt) const override
 Get the nondimensional Enthalpy functions for the species at their standard states at the current T and P of the solution.
 
void getEntropy_R (double *sr) const override
 Get the array of nondimensional Entropy functions for the standard state species at the current T and P of the solution.
 
void getGibbs_RT (double *grt) const override
 Get the nondimensional Gibbs functions for the species in their standard states at the current T and P of the solution.
 
void getPureGibbs (double *gpure) const override
 Get the Gibbs functions for the standard state of the species at the current T and P of the solution.
 
void getIntEnergy_RT (double *urt) const override
 Returns the vector of nondimensional Internal Energies of the standard state species at the current T and P of the solution.
 
void getCp_R (double *cpr) const override
 Get the nondimensional Heat Capacities at constant pressure for the species standard states at the current T and P of the solution.
 
void getStandardVolumes (double *vol) const override
 Get the molar volumes of the species standard states at the current T and P of the solution.
 
virtual const vector< double > & getStandardVolumes () const
 
void initThermo () override
 Initialize the ThermoPhase object after all species have been set up.
 
void getSpeciesParameters (const string &name, AnyMap &speciesNode) const override
 Get phase-specific parameters of a Species object such that an identical one could be reconstructed and added to this phase.
 
bool addSpecies (shared_ptr< Species > spec) override
 Add a Species to this Phase.
 
void installPDSS (size_t k, unique_ptr< PDSS > &&pdss)
 Install a PDSS object for species k
 
virtual bool addSpecies (shared_ptr< Species > spec)
 Add a Species to this Phase.
 
void getEnthalpy_RT_ref (double *hrt) const override
 Returns the vector of nondimensional enthalpies of the reference state at the current temperature of the solution and the reference pressure for the species.
 
void getGibbs_RT_ref (double *grt) const override
 Returns the vector of nondimensional Gibbs Free Energies of the reference state at the current temperature of the solution and the reference pressure for the species.
 
void getGibbs_ref (double *g) const override
 Returns the vector of the Gibbs function of the reference state at the current temperature of the solution and the reference pressure for the species.
 
void getEntropy_R_ref (double *er) const override
 Returns the vector of nondimensional entropies of the reference state at the current temperature of the solution and the reference pressure for each species.
 
void getCp_R_ref (double *cprt) const override
 Returns the vector of nondimensional constant pressure heat capacities of the reference state at the current temperature of the solution and reference pressure for each species.
 
void getStandardVolumes_ref (double *vol) const override
 Get the molar volumes of the species reference states at the current T and P_ref of the solution.
 
- Public Member Functions inherited from ThermoPhase
 ThermoPhase ()=default
 Constructor.
 
double RT () const
 Return the Gas Constant multiplied by the current temperature.
 
double equivalenceRatio () const
 Compute the equivalence ratio for the current mixture from available oxygen and required oxygen.
 
string type () const override
 String indicating the thermodynamic model implemented.
 
virtual bool isIdeal () const
 Boolean indicating whether phase is ideal.
 
virtual string phaseOfMatter () const
 String indicating the mechanical phase of the matter in this Phase.
 
virtual double refPressure () const
 Returns the reference pressure in Pa.
 
double Hf298SS (const size_t k) const
 Report the 298 K Heat of Formation of the standard state of one species (J kmol-1)
 
virtual void modifyOneHf298SS (const size_t k, const double Hf298New)
 Modify the value of the 298 K Heat of Formation of one species in the phase (J kmol-1)
 
virtual void resetHf298 (const size_t k=npos)
 Restore the original heat of formation of one or more species.
 
bool chargeNeutralityNecessary () const
 Returns the chargeNeutralityNecessity boolean.
 
virtual double enthalpy_mole () const
 Molar enthalpy. Units: J/kmol.
 
virtual double intEnergy_mole () const
 Molar internal energy. Units: J/kmol.
 
virtual double entropy_mole () const
 Molar entropy. Units: J/kmol/K.
 
virtual double gibbs_mole () const
 Molar Gibbs function. Units: J/kmol.
 
virtual double cp_mole () const
 Molar heat capacity at constant pressure. Units: J/kmol/K.
 
virtual double cv_mole () const
 Molar heat capacity at constant volume. Units: J/kmol/K.
 
virtual double isothermalCompressibility () const
 Returns the isothermal compressibility. Units: 1/Pa.
 
virtual double thermalExpansionCoeff () const
 Return the volumetric thermal expansion coefficient. Units: 1/K.
 
virtual double soundSpeed () const
 Return the speed of sound. Units: m/s.
 
void setElectricPotential (double v)
 Set the electric potential of this phase (V).
 
double electricPotential () const
 Returns the electric potential of this phase (V).
 
virtual int activityConvention () const
 This method returns the convention used in specification of the activities, of which there are currently two, molar- and molality-based conventions.
 
virtual void getLnActivityCoefficients (double *lnac) const
 Get the array of non-dimensional molar-based ln activity coefficients at the current solution temperature, pressure, and solution concentration.
 
virtual void getChemPotentials (double *mu) const
 Get the species chemical potentials. Units: J/kmol.
 
void getElectrochemPotentials (double *mu) const
 Get the species electrochemical potentials.
 
virtual void getPartialMolarEnthalpies (double *hbar) const
 Returns an array of partial molar enthalpies for the species in the mixture.
 
virtual void getPartialMolarEntropies (double *sbar) const
 Returns an array of partial molar entropies of the species in the solution.
 
virtual void getPartialMolarIntEnergies (double *ubar) const
 Return an array of partial molar internal energies for the species in the mixture.
 
virtual void getPartialMolarCp (double *cpbar) const
 Return an array of partial molar heat capacities for the species in the mixture.
 
virtual void getIntEnergy_RT_ref (double *urt) const
 Returns the vector of nondimensional internal Energies of the reference state at the current temperature of the solution and the reference pressure for each species.
 
double enthalpy_mass () const
 Specific enthalpy. Units: J/kg.
 
double intEnergy_mass () const
 Specific internal energy. Units: J/kg.
 
double entropy_mass () const
 Specific entropy. Units: J/kg/K.
 
double gibbs_mass () const
 Specific Gibbs function. Units: J/kg.
 
double cp_mass () const
 Specific heat at constant pressure. Units: J/kg/K.
 
double cv_mass () const
 Specific heat at constant volume. Units: J/kg/K.
 
virtual void setState_TPX (double t, double p, const double *x)
 Set the temperature (K), pressure (Pa), and mole fractions.
 
virtual void setState_TPX (double t, double p, const Composition &x)
 Set the temperature (K), pressure (Pa), and mole fractions.
 
virtual void setState_TPX (double t, double p, const string &x)
 Set the temperature (K), pressure (Pa), and mole fractions.
 
virtual void setState_TPY (double t, double p, const double *y)
 Set the internally stored temperature (K), pressure (Pa), and mass fractions of the phase.
 
virtual void setState_TPY (double t, double p, const Composition &y)
 Set the internally stored temperature (K), pressure (Pa), and mass fractions of the phase.
 
virtual void setState_TPY (double t, double p, const string &y)
 Set the internally stored temperature (K), pressure (Pa), and mass fractions of the phase.
 
virtual void setState_HP (double h, double p, double tol=1e-9)
 Set the internally stored specific enthalpy (J/kg) and pressure (Pa) of the phase.
 
virtual void setState_UV (double u, double v, double tol=1e-9)
 Set the specific internal energy (J/kg) and specific volume (m^3/kg).
 
virtual void setState_SP (double s, double p, double tol=1e-9)
 Set the specific entropy (J/kg/K) and pressure (Pa).
 
virtual void setState_SV (double s, double v, double tol=1e-9)
 Set the specific entropy (J/kg/K) and specific volume (m^3/kg).
 
virtual void setState_ST (double s, double t, double tol=1e-9)
 Set the specific entropy (J/kg/K) and temperature (K).
 
virtual void setState_TV (double t, double v, double tol=1e-9)
 Set the temperature (K) and specific volume (m^3/kg).
 
virtual void setState_PV (double p, double v, double tol=1e-9)
 Set the pressure (Pa) and specific volume (m^3/kg).
 
virtual void setState_UP (double u, double p, double tol=1e-9)
 Set the specific internal energy (J/kg) and pressure (Pa).
 
virtual void setState_VH (double v, double h, double tol=1e-9)
 Set the specific volume (m^3/kg) and the specific enthalpy (J/kg)
 
virtual void setState_TH (double t, double h, double tol=1e-9)
 Set the temperature (K) and the specific enthalpy (J/kg)
 
virtual void setState_SH (double s, double h, double tol=1e-9)
 Set the specific entropy (J/kg/K) and the specific enthalpy (J/kg)
 
virtual void setState_DP (double rho, double p)
 Set the density (kg/m**3) and pressure (Pa) at constant composition.
 
virtual void setState (const AnyMap &state)
 Set the state using an AnyMap containing any combination of properties supported by the thermodynamic model.
 
void setMixtureFraction (double mixFrac, const double *fuelComp, const double *oxComp, ThermoBasis basis=ThermoBasis::molar)
 Set the mixture composition according to the mixture fraction = kg fuel / (kg oxidizer + kg fuel)
 
void setMixtureFraction (double mixFrac, const string &fuelComp, const string &oxComp, ThermoBasis basis=ThermoBasis::molar)
 Set the mixture composition according to the mixture fraction = kg fuel / (kg oxidizer + kg fuel)
 
void setMixtureFraction (double mixFrac, const Composition &fuelComp, const Composition &oxComp, ThermoBasis basis=ThermoBasis::molar)
 Set the mixture composition according to the mixture fraction = kg fuel / (kg oxidizer + kg fuel)
 
double mixtureFraction (const double *fuelComp, const double *oxComp, ThermoBasis basis=ThermoBasis::molar, const string &element="Bilger") const
 Compute the mixture fraction = kg fuel / (kg oxidizer + kg fuel) for the current mixture given fuel and oxidizer compositions.
 
double mixtureFraction (const string &fuelComp, const string &oxComp, ThermoBasis basis=ThermoBasis::molar, const string &element="Bilger") const
 Compute the mixture fraction = kg fuel / (kg oxidizer + kg fuel) for the current mixture given fuel and oxidizer compositions.
 
double mixtureFraction (const Composition &fuelComp, const Composition &oxComp, ThermoBasis basis=ThermoBasis::molar, const string &element="Bilger") const
 Compute the mixture fraction = kg fuel / (kg oxidizer + kg fuel) for the current mixture given fuel and oxidizer compositions.
 
void setEquivalenceRatio (double phi, const double *fuelComp, const double *oxComp, ThermoBasis basis=ThermoBasis::molar)
 Set the mixture composition according to the equivalence ratio.
 
void setEquivalenceRatio (double phi, const string &fuelComp, const string &oxComp, ThermoBasis basis=ThermoBasis::molar)
 Set the mixture composition according to the equivalence ratio.
 
void setEquivalenceRatio (double phi, const Composition &fuelComp, const Composition &oxComp, ThermoBasis basis=ThermoBasis::molar)
 Set the mixture composition according to the equivalence ratio.
 
double equivalenceRatio (const double *fuelComp, const double *oxComp, ThermoBasis basis=ThermoBasis::molar) const
 Compute the equivalence ratio for the current mixture given the compositions of fuel and oxidizer.
 
double equivalenceRatio (const string &fuelComp, const string &oxComp, ThermoBasis basis=ThermoBasis::molar) const
 Compute the equivalence ratio for the current mixture given the compositions of fuel and oxidizer.
 
double equivalenceRatio (const Composition &fuelComp, const Composition &oxComp, ThermoBasis basis=ThermoBasis::molar) const
 Compute the equivalence ratio for the current mixture given the compositions of fuel and oxidizer.
 
double stoichAirFuelRatio (const double *fuelComp, const double *oxComp, ThermoBasis basis=ThermoBasis::molar) const
 Compute the stoichiometric air to fuel ratio (kg oxidizer / kg fuel) given fuel and oxidizer compositions.
 
double stoichAirFuelRatio (const string &fuelComp, const string &oxComp, ThermoBasis basis=ThermoBasis::molar) const
 Compute the stoichiometric air to fuel ratio (kg oxidizer / kg fuel) given fuel and oxidizer compositions.
 
double stoichAirFuelRatio (const Composition &fuelComp, const Composition &oxComp, ThermoBasis basis=ThermoBasis::molar) const
 Compute the stoichiometric air to fuel ratio (kg oxidizer / kg fuel) given fuel and oxidizer compositions.
 
void equilibrate (const string &XY, const string &solver="auto", double rtol=1e-9, int max_steps=50000, int max_iter=100, int estimate_equil=0, int log_level=0)
 Equilibrate a ThermoPhase object.
 
virtual void setToEquilState (const double *mu_RT)
 This method is used by the ChemEquil equilibrium solver.
 
virtual bool compatibleWithMultiPhase () const
 Indicates whether this phase type can be used with class MultiPhase for equilibrium calculations.
 
virtual double critTemperature () const
 Critical temperature (K).
 
virtual double critPressure () const
 Critical pressure (Pa).
 
virtual double critVolume () const
 Critical volume (m3/kmol).
 
virtual double critCompressibility () const
 Critical compressibility (unitless).
 
virtual double critDensity () const
 Critical density (kg/m3).
 
virtual double satTemperature (double p) const
 Return the saturation temperature given the pressure.
 
virtual double satPressure (double t)
 Return the saturation pressure given the temperature.
 
virtual double vaporFraction () const
 Return the fraction of vapor at the current conditions.
 
virtual void setState_Tsat (double t, double x)
 Set the state to a saturated system at a particular temperature.
 
virtual void setState_Psat (double p, double x)
 Set the state to a saturated system at a particular pressure.
 
void setState_TPQ (double T, double P, double Q)
 Set the temperature, pressure, and vapor fraction (quality).
 
void modifySpecies (size_t k, shared_ptr< Species > spec) override
 Modify the thermodynamic data associated with a species.
 
virtual MultiSpeciesThermospeciesThermo (int k=-1)
 Return a changeable reference to the calculation manager for species reference-state thermodynamic properties.
 
virtual const MultiSpeciesThermospeciesThermo (int k=-1) const
 
void initThermoFile (const string &inputFile, const string &id)
 Initialize a ThermoPhase object using an input file.
 
virtual void setParameters (const AnyMap &phaseNode, const AnyMap &rootNode=AnyMap())
 Set equation of state parameters from an AnyMap phase description.
 
AnyMap parameters (bool withInput=true) const
 Returns the parameters of a ThermoPhase object such that an identical one could be reconstructed using the newThermo(AnyMap&) function.
 
const AnyMapinput () const
 Access input data associated with the phase description.
 
AnyMapinput ()
 
virtual void getdlnActCoeffds (const double dTds, const double *const dXds, double *dlnActCoeffds) const
 Get the change in activity coefficients wrt changes in state (temp, mole fraction, etc) along a line in parameter space or along a line in physical space.
 
virtual void getdlnActCoeffdlnX_diag (double *dlnActCoeffdlnX_diag) const
 Get the array of ln mole fraction derivatives of the log activity coefficients - diagonal component only.
 
virtual void getdlnActCoeffdlnN_diag (double *dlnActCoeffdlnN_diag) const
 Get the array of log species mole number derivatives of the log activity coefficients.
 
virtual void getdlnActCoeffdlnN_numderiv (const size_t ld, double *const dlnActCoeffdlnN)
 
virtual string report (bool show_thermo=true, double threshold=-1e-14) const
 returns a summary of the state of the phase as a string
 
- Public Member Functions inherited from Phase
 Phase ()=default
 Default constructor.
 
 Phase (const Phase &)=delete
 
Phaseoperator= (const Phase &)=delete
 
virtual bool isPure () const
 Return whether phase represents a pure (single species) substance.
 
virtual bool hasPhaseTransition () const
 Return whether phase represents a substance with phase transitions.
 
virtual bool isCompressible () const
 Return whether phase represents a compressible substance.
 
virtual map< string, size_t > nativeState () const
 Return a map of properties defining the native state of a substance.
 
string nativeMode () const
 Return string acronym representing the native state of a Phase.
 
virtual vector< string > fullStates () const
 Return a vector containing full states defining a phase.
 
virtual vector< string > partialStates () const
 Return a vector of settable partial property sets within a phase.
 
virtual size_t stateSize () const
 Return size of vector defining internal state of the phase.
 
void saveState (vector< double > &state) const
 Save the current internal state of the phase.
 
virtual void saveState (size_t lenstate, double *state) const
 Write to array 'state' the current internal state.
 
void restoreState (const vector< double > &state)
 Restore a state saved on a previous call to saveState.
 
virtual void restoreState (size_t lenstate, const double *state)
 Restore the state of the phase from a previously saved state vector.
 
double molecularWeight (size_t k) const
 Molecular weight of species k.
 
void getMolecularWeights (double *weights) const
 Copy the vector of molecular weights into array weights.
 
const vector< double > & molecularWeights () const
 Return a const reference to the internal vector of molecular weights.
 
const vector< double > & inverseMolecularWeights () const
 Return a const reference to the internal vector of molecular weights.
 
void getCharges (double *charges) const
 Copy the vector of species charges into array charges.
 
virtual void setMolesNoTruncate (const double *const N)
 Set the state of the object with moles in [kmol].
 
double elementalMassFraction (const size_t m) const
 Elemental mass fraction of element m.
 
double elementalMoleFraction (const size_t m) const
 Elemental mole fraction of element m.
 
double charge (size_t k) const
 Dimensionless electrical charge of a single molecule of species k The charge is normalized by the the magnitude of the electron charge.
 
double chargeDensity () const
 Charge density [C/m^3].
 
size_t nDim () const
 Returns the number of spatial dimensions (1, 2, or 3)
 
void setNDim (size_t ndim)
 Set the number of spatial dimensions (1, 2, or 3).
 
virtual bool ready () const
 Returns a bool indicating whether the object is ready for use.
 
int stateMFNumber () const
 Return the State Mole Fraction Number.
 
virtual void invalidateCache ()
 Invalidate any cached values which are normally updated only when a change in state is detected.
 
bool caseSensitiveSpecies () const
 Returns true if case sensitive species names are enforced.
 
void setCaseSensitiveSpecies (bool cflag=true)
 Set flag that determines whether case sensitive species are enforced in look-up operations, for example speciesIndex.
 
vector< double > getCompositionFromMap (const Composition &comp) const
 Converts a Composition to a vector with entries for each species Species that are not specified are set to zero in the vector.
 
void massFractionsToMoleFractions (const double *Y, double *X) const
 Converts a mixture composition from mole fractions to mass fractions.
 
void moleFractionsToMassFractions (const double *X, double *Y) const
 Converts a mixture composition from mass fractions to mole fractions.
 
string name () const
 Return the name of the phase.
 
void setName (const string &nm)
 Sets the string name for the phase.
 
string elementName (size_t m) const
 Name of the element with index m.
 
size_t elementIndex (const string &name) const
 Return the index of element named 'name'.
 
const vector< string > & elementNames () const
 Return a read-only reference to the vector of element names.
 
double atomicWeight (size_t m) const
 Atomic weight of element m.
 
double entropyElement298 (size_t m) const
 Entropy of the element in its standard state at 298 K and 1 bar.
 
int atomicNumber (size_t m) const
 Atomic number of element m.
 
int elementType (size_t m) const
 Return the element constraint type Possible types include:
 
int changeElementType (int m, int elem_type)
 Change the element type of the mth constraint Reassigns an element type.
 
const vector< double > & atomicWeights () const
 Return a read-only reference to the vector of atomic weights.
 
size_t nElements () const
 Number of elements.
 
void checkElementIndex (size_t m) const
 Check that the specified element index is in range.
 
void checkElementArraySize (size_t mm) const
 Check that an array size is at least nElements().
 
double nAtoms (size_t k, size_t m) const
 Number of atoms of element m in species k.
 
size_t speciesIndex (const string &name) const
 Returns the index of a species named 'name' within the Phase object.
 
string speciesName (size_t k) const
 Name of the species with index k.
 
const vector< string > & speciesNames () const
 Return a const reference to the vector of species names.
 
size_t nSpecies () const
 Returns the number of species in the phase.
 
void checkSpeciesIndex (size_t k) const
 Check that the specified species index is in range.
 
void checkSpeciesArraySize (size_t kk) const
 Check that an array size is at least nSpecies().
 
void setMoleFractionsByName (const Composition &xMap)
 Set the species mole fractions by name.
 
void setMoleFractionsByName (const string &x)
 Set the mole fractions of a group of species by name.
 
void setMassFractionsByName (const Composition &yMap)
 Set the species mass fractions by name.
 
void setMassFractionsByName (const string &x)
 Set the species mass fractions by name.
 
void setState_TD (double t, double rho)
 Set the internally stored temperature (K) and density (kg/m^3)
 
Composition getMoleFractionsByName (double threshold=0.0) const
 Get the mole fractions by name.
 
double moleFraction (size_t k) const
 Return the mole fraction of a single species.
 
double moleFraction (const string &name) const
 Return the mole fraction of a single species.
 
Composition getMassFractionsByName (double threshold=0.0) const
 Get the mass fractions by name.
 
double massFraction (size_t k) const
 Return the mass fraction of a single species.
 
double massFraction (const string &name) const
 Return the mass fraction of a single species.
 
void getMoleFractions (double *const x) const
 Get the species mole fraction vector.
 
virtual void setMoleFractions (const double *const x)
 Set the mole fractions to the specified values.
 
virtual void setMoleFractions_NoNorm (const double *const x)
 Set the mole fractions to the specified values without normalizing.
 
void getMassFractions (double *const y) const
 Get the species mass fractions.
 
const double * massFractions () const
 Return a const pointer to the mass fraction array.
 
virtual void setMassFractions (const double *const y)
 Set the mass fractions to the specified values and normalize them.
 
virtual void setMassFractions_NoNorm (const double *const y)
 Set the mass fractions to the specified values without normalizing.
 
virtual void getConcentrations (double *const c) const
 Get the species concentrations (kmol/m^3).
 
virtual double concentration (const size_t k) const
 Concentration of species k.
 
virtual void setConcentrations (const double *const conc)
 Set the concentrations to the specified values within the phase.
 
virtual void setConcentrationsNoNorm (const double *const conc)
 Set the concentrations without ignoring negative concentrations.
 
double temperature () const
 Temperature (K).
 
virtual double electronTemperature () const
 Electron Temperature (K)
 
virtual double density () const
 Density (kg/m^3).
 
virtual double molarDensity () const
 Molar density (kmol/m^3).
 
virtual double molarVolume () const
 Molar volume (m^3/kmol).
 
virtual void setDensity (const double density_)
 Set the internally stored density (kg/m^3) of the phase.
 
virtual void setElectronTemperature (double etemp)
 Set the internally stored electron temperature of the phase (K).
 
double mean_X (const double *const Q) const
 Evaluate the mole-fraction-weighted mean of an array Q.
 
double mean_X (const vector< double > &Q) const
 Evaluate the mole-fraction-weighted mean of an array Q.
 
double meanMolecularWeight () const
 The mean molecular weight. Units: (kg/kmol)
 
double sum_xlogx () const
 Evaluate \( \sum_k X_k \ln X_k \).
 
size_t addElement (const string &symbol, double weight=-12345.0, int atomicNumber=0, double entropy298=ENTROPY298_UNKNOWN, int elem_type=CT_ELEM_TYPE_ABSPOS)
 Add an element.
 
void addSpeciesAlias (const string &name, const string &alias)
 Add a species alias (that is, a user-defined alternative species name).
 
virtual vector< string > findIsomers (const Composition &compMap) const
 Return a vector with isomers names matching a given composition map.
 
virtual vector< string > findIsomers (const string &comp) const
 Return a vector with isomers names matching a given composition string.
 
shared_ptr< Speciesspecies (const string &name) const
 Return the Species object for the named species.
 
shared_ptr< Speciesspecies (size_t k) const
 Return the Species object for species whose index is k.
 
void ignoreUndefinedElements ()
 Set behavior when adding a species containing undefined elements to just skip the species.
 
void addUndefinedElements ()
 Set behavior when adding a species containing undefined elements to add those elements to the phase.
 
void throwUndefinedElements ()
 Set the behavior when adding a species containing undefined elements to throw an exception.
 

Protected Member Functions

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

Protected Attributes

vector< double > moleFractions_
 Storage for the current values of the mole fractions of the species.
 
vector< double > lnActCoeff_Scaled_
 Storage for the current values of the activity coefficients of the species.
 
vector< double > dlnActCoeffdT_Scaled_
 Storage for the current derivative values of the gradients with respect to temperature of the log of the activity coefficients of the species.
 
vector< double > d2lnActCoeffdT2_Scaled_
 Storage for the current derivative values of the gradients with respect to temperature of the log of the activity coefficients of the species.
 
vector< double > dlnActCoeffdlnN_diag_
 Storage for the current derivative values of the gradients with respect to logarithm of the mole fraction of the log of the activity coefficients of the species.
 
vector< double > dlnActCoeffdlnX_diag_
 Storage for the current derivative values of the gradients with respect to logarithm of the mole fraction of the log of the activity coefficients of the species.
 
Array2D dlnActCoeffdlnN_
 Storage for the current derivative values of the gradients with respect to logarithm of the species mole number of the log of the activity coefficients of the species.
 
- Protected Attributes inherited from VPStandardStateTP
double m_Pcurrent = OneAtm
 Current value of the pressure - state variable.
 
double m_minTemp = 0.0
 The minimum temperature at which data for all species is valid.
 
double m_maxTemp = BigNumber
 The maximum temperature at which data for all species is valid.
 
double m_Tlast_ss = -1.0
 The last temperature at which the standard state thermodynamic properties were calculated at.
 
double m_Plast_ss = -1.0
 The last pressure at which the Standard State thermodynamic properties were calculated at.
 
vector< unique_ptr< PDSS > > m_PDSS_storage
 Storage for the PDSS objects for the species.
 
vector< double > m_h0_RT
 Vector containing the species reference enthalpies at T = m_tlast and P = p_ref.
 
vector< double > m_cp0_R
 Vector containing the species reference constant pressure heat capacities at T = m_tlast and P = p_ref.
 
vector< double > m_g0_RT
 Vector containing the species reference Gibbs functions at T = m_tlast and P = p_ref.
 
vector< double > m_s0_R
 Vector containing the species reference entropies at T = m_tlast and P = p_ref.
 
vector< double > m_V0
 Vector containing the species reference molar volumes.
 
vector< double > m_hss_RT
 Vector containing the species Standard State enthalpies at T = m_tlast and P = m_plast.
 
vector< double > m_cpss_R
 Vector containing the species Standard State constant pressure heat capacities at T = m_tlast and P = m_plast.
 
vector< double > m_gss_RT
 Vector containing the species Standard State Gibbs functions at T = m_tlast and P = m_plast.
 
vector< double > m_sss_R
 Vector containing the species Standard State entropies at T = m_tlast and P = m_plast.
 
vector< double > m_Vss
 Vector containing the species standard state volumes at T = m_tlast and P = m_plast.
 
- Protected Attributes inherited from ThermoPhase
MultiSpeciesThermo m_spthermo
 Pointer to the calculation manager for species reference-state thermodynamic properties.
 
AnyMap m_input
 Data supplied via setParameters.
 
double m_phi = 0.0
 Stored value of the electric potential for this phase. Units are Volts.
 
bool m_chargeNeutralityNecessary = false
 Boolean indicating whether a charge neutrality condition is a necessity.
 
int m_ssConvention = cSS_CONVENTION_TEMPERATURE
 Contains the standard state convention.
 
double m_tlast = 0.0
 last value of the temperature processed by reference state
 
- Protected Attributes inherited from Phase
ValueCache m_cache
 Cached for saved calculations within each ThermoPhase.
 
size_t m_kk = 0
 Number of species in the phase.
 
size_t m_ndim = 3
 Dimensionality of the phase.
 
vector< double > m_speciesComp
 Atomic composition of the species.
 
vector< double > m_speciesCharge
 Vector of species charges. length m_kk.
 
map< string, shared_ptr< Species > > m_species
 
UndefElement::behavior m_undefinedElementBehavior = UndefElement::add
 Flag determining behavior when adding species with an undefined element.
 
bool m_caseSensitiveSpecies = false
 Flag determining whether case sensitive species names are enforced.
 

Constructor & Destructor Documentation

◆ GibbsExcessVPSSTP()

GibbsExcessVPSSTP ( )
inline

Definition at line 90 of file GibbsExcessVPSSTP.h.

Member Function Documentation

◆ calcDensity()

void calcDensity ( )
overrideprotectedvirtual

Calculate the density of the mixture using the partial molar volumes and mole fractions as input.

The formula for this is

\[ \rho = \frac{\sum_k{X_k W_k}}{\sum_k{X_k V_k}} \]

where \( X_k \) are the mole fractions, \( W_k \) are the molecular weights, and \( V_k \) are the pure species molar volumes.

Note, the basis behind this formula is that in an ideal solution the partial molar volumes are equal to the pure species molar volumes. We have additionally specified in this class that the pure species molar volumes are independent of temperature and pressure.

NOTE: This function is not a member of the ThermoPhase base class.

Reimplemented from VPStandardStateTP.

Definition at line 32 of file GibbsExcessVPSSTP.cpp.

◆ standardConcentrationUnits()

Units standardConcentrationUnits ( ) const
overridevirtual

Returns the units of the "standard concentration" for this phase.

These are the units of the values returned by the functions getActivityConcentrations() and standardConcentration(), which can vary between different ThermoPhase-derived classes, or change within a single class depending on input options. See the documentation for standardConcentration() for the derived class for specific details.

Reimplemented from ThermoPhase.

Definition at line 45 of file GibbsExcessVPSSTP.cpp.

◆ getActivityConcentrations()

void getActivityConcentrations ( double *  c) const
overridevirtual

This method returns an array of generalized concentrations.

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

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

Reimplemented from ThermoPhase.

Definition at line 50 of file GibbsExcessVPSSTP.cpp.

◆ standardConcentration()

double standardConcentration ( size_t  k = 0) const
overridevirtual

The standard concentration \( C^0_k \) used to normalize the 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 (for example, surface species of different sizes), this method may be called with an optional parameter indicating the species.

The standard concentration for defaulted to 1. In other words the activity concentration is assumed to be 1.

Parameters
kspecies index. Defaults to zero.

Reimplemented from ThermoPhase.

Definition at line 55 of file GibbsExcessVPSSTP.cpp.

◆ logStandardConc()

double logStandardConc ( size_t  k = 0) const
overridevirtual

Natural logarithm of the standard concentration of the kth species.

Parameters
kindex of the species (defaults to zero)

Reimplemented from ThermoPhase.

Definition at line 60 of file GibbsExcessVPSSTP.cpp.

◆ getActivities()

void getActivities ( double *  ac) const
overridevirtual

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

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

This function must be implemented in derived classes.

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

Reimplemented from ThermoPhase.

Definition at line 65 of file GibbsExcessVPSSTP.cpp.

◆ getActivityCoefficients()

void getActivityCoefficients ( double *  ac) const
overridevirtual

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

Parameters
acOutput vector of activity coefficients. Length: m_kk.

Reimplemented from ThermoPhase.

Definition at line 74 of file GibbsExcessVPSSTP.cpp.

◆ getdlnActCoeffdT()

virtual void getdlnActCoeffdT ( double *  dlnActCoeffdT) const
inlinevirtual

Get the array of temperature derivatives of the log activity coefficients.

units = 1/Kelvin

Parameters
dlnActCoeffdTOutput vector of temperature derivatives of the log Activity Coefficients. length = m_kk

Reimplemented in MargulesVPSSTP, and RedlichKisterVPSSTP.

Definition at line 154 of file GibbsExcessVPSSTP.h.

◆ getdlnActCoeffdlnN()

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

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

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

units = 1 / kmol

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

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

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

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

Reimplemented from ThermoPhase.

Reimplemented in MargulesVPSSTP, and RedlichKisterVPSSTP.

Definition at line 158 of file GibbsExcessVPSSTP.h.

◆ getdlnActCoeffdlnX()

virtual void getdlnActCoeffdlnX ( double *  dlnActCoeffdlnX) const
inlinevirtual

Get the array of log concentration-like derivatives of the log activity coefficients.

This function is a virtual method. For ideal mixtures (unity activity coefficients), this can return zero. Implementations should take the derivative of the logarithm of the activity coefficient with respect to the logarithm of the concentration-like variable (for example, number of moles in in a unit volume. ) that represents the standard state. This quantity is to be used in conjunction with derivatives of that concentration-like variable when the derivative of the chemical potential is taken.

units = dimensionless

Parameters
dlnActCoeffdlnXOutput vector of derivatives of the log Activity Coefficients. length = m_kk

Definition at line 179 of file GibbsExcessVPSSTP.h.

◆ getPartialMolarVolumes()

void getPartialMolarVolumes ( double *  vbar) const
overridevirtual

Return an array of partial molar volumes for the species in the mixture.

Units: m^3/kmol.

Frequently, for this class of thermodynamics representations, the excess Volume due to mixing is zero. Here, we set it as a default. It may be overridden in derived classes.

Parameters
vbarOutput vector of species partial molar volumes. Length = m_kk. units are m^3/kmol.

Reimplemented from ThermoPhase.

Reimplemented in MargulesVPSSTP, and RedlichKisterVPSSTP.

Definition at line 90 of file GibbsExcessVPSSTP.cpp.

◆ addSpecies()

bool addSpecies ( shared_ptr< Species spec)
overridevirtual

Add a Species to this Phase.

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

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

See also
ignoreUndefinedElements addUndefinedElements throwUndefinedElements

Reimplemented from Phase.

Definition at line 96 of file GibbsExcessVPSSTP.cpp.

◆ compositionChanged()

void compositionChanged ( )
overrideprotectedvirtual

Apply changes to the state which are needed after the composition changes.

This function is called after any call to setMassFractions(), setMoleFractions(), or similar. For phases which need to execute a callback after any change to the composition, it should be done by overriding this function rather than overriding all of the composition- setting functions. Derived class implementations of compositionChanged() should call the parent class method as well.

Reimplemented from Phase.

Definition at line 24 of file GibbsExcessVPSSTP.cpp.

Member Data Documentation

◆ moleFractions_

vector<double> moleFractions_
mutableprotected

Storage for the current values of the mole fractions of the species.

This vector is kept up-to-date when the setState functions are called. Therefore, it may be considered to be an independent variable.

Note in order to do this, the setState functions are redefined to always keep this vector current.

Definition at line 213 of file GibbsExcessVPSSTP.h.

◆ lnActCoeff_Scaled_

vector<double> lnActCoeff_Scaled_
mutableprotected

Storage for the current values of the activity coefficients of the species.

Definition at line 217 of file GibbsExcessVPSSTP.h.

◆ dlnActCoeffdT_Scaled_

vector<double> dlnActCoeffdT_Scaled_
mutableprotected

Storage for the current derivative values of the gradients with respect to temperature of the log of the activity coefficients of the species.

Definition at line 221 of file GibbsExcessVPSSTP.h.

◆ d2lnActCoeffdT2_Scaled_

vector<double> d2lnActCoeffdT2_Scaled_
mutableprotected

Storage for the current derivative values of the gradients with respect to temperature of the log of the activity coefficients of the species.

Definition at line 225 of file GibbsExcessVPSSTP.h.

◆ dlnActCoeffdlnN_diag_

vector<double> dlnActCoeffdlnN_diag_
mutableprotected

Storage for the current derivative values of the gradients with respect to logarithm of the mole fraction of the log of the activity coefficients of the species.

Definition at line 230 of file GibbsExcessVPSSTP.h.

◆ dlnActCoeffdlnX_diag_

vector<double> dlnActCoeffdlnX_diag_
mutableprotected

Storage for the current derivative values of the gradients with respect to logarithm of the mole fraction of the log of the activity coefficients of the species.

Definition at line 235 of file GibbsExcessVPSSTP.h.

◆ dlnActCoeffdlnN_

Array2D dlnActCoeffdlnN_
mutableprotected

Storage for the current derivative values of the gradients with respect to logarithm of the species mole number of the log of the activity coefficients of the species.

dlnActCoeffdlnN_(k, m) is the derivative of ln(gamma_k) wrt ln mole number of species m

Definition at line 244 of file GibbsExcessVPSSTP.h.


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