MargulesVPSSTP is a derived class of GibbsExcessVPSSTP that employs the Margules approximation for the excess Gibbs free energy. More...

#include <MargulesVPSSTP.h>

Inheritance diagram for MargulesVPSSTP:

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Collaboration diagram for MargulesVPSSTP:

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Public Member Functions
	MargulesVPSSTP (const std::string &inputFile, const std::string &id="")
	Construct a MargulesVPSSTP object from an input file. More...

	MargulesVPSSTP (XML_Node &phaseRef, const std::string &id="")
	Construct and initialize a MargulesVPSSTP ThermoPhase object directly from an XML database. More...

virtual std::string	type () const
	String indicating the thermodynamic model implemented. More...

Molar Thermodynamic Properties
virtual doublereal	enthalpy_mole () const
	Molar enthalpy. Units: J/kmol. More...

virtual doublereal	entropy_mole () const
	Molar entropy. Units: J/kmol/K. 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...

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.
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...

Partial Molar Properties of the Solution
virtual void	getChemPotentials (doublereal *mu) const
	Get the species chemical potentials. Units: J/kmol. 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 for the species in the mixture. More...

virtual void	getPartialMolarCp (doublereal *cpbar) const
	Returns an array of partial molar entropies 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	getd2lnActCoeffdT2 (doublereal *d2lnActCoeffdT2) const
	Get the array of temperature second derivatives of the log activity coefficients. More...

virtual void	getdlnActCoeffdT (doublereal *dlnActCoeffdT) const
	Get the array of temperature derivatives of the log activity coefficients. 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 void	initThermo ()

virtual void	initThermoXML (XML_Node &phaseNode, const std::string &id)
	Import and initialize a ThermoPhase object using an XML tree. More...

void	addBinaryInteraction (const std::string &speciesA, const std::string &speciesB, double h0, double h1, double s0, double s1, double vh0, double vh1, double vs0, double vs1)
	Add a binary species interaction with the specified parameters. More...

Public Member Functions inherited from GibbsExcessVPSSTP
	GibbsExcessVPSSTP ()

virtual Units	standardConcentrationUnits () const
	Returns the units of the "standard concentration" for this phase. More...

virtual void	getActivityConcentrations (doublereal *c) const
	This method returns an array of generalized concentrations. More...

virtual doublereal	standardConcentration (size_t k=0) const
	The standard concentration \( C^0_k \) used to normalize the generalized concentration. More...

virtual doublereal	logStandardConc (size_t k=0) const
	Natural logarithm of the standard concentration of 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 molar-based activity coefficients at the current solution temperature, pressure, and solution concentration. More...

virtual void	getdlnActCoeffdlnX (doublereal *dlnActCoeffdlnX) const
	Get the array of log concentration-like derivatives of the log activity coefficients. More...

virtual const vector_fp &	getPartialMolarVolumesVector () const

virtual bool	addSpecies (shared_ptr< Species > spec)

Public Member Functions inherited from VPStandardStateTP
	VPStandardStateTP ()
	Constructor. More...

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	getChemPotentials_RT (doublereal *mu) const
	Get the array of non-dimensional species chemical potentials. More...

void	installPDSS (size_t k, std::unique_ptr< PDSS > &&pdss)
	Install a PDSS object for species k More...

PDSS *	providePDSS (size_t k)

const PDSS *	providePDSS (size_t k) const

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

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...

virtual std::string	phaseOfMatter () const
	String indicating the mechanical phase of the matter in this Phase. 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	intEnergy_mole () const
	Molar internal energy. Units: J/kmol. More...

virtual doublereal	gibbs_mole () const
	Molar Gibbs function. Units: J/kmol. 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 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. More...

void	getElectrochemPotentials (doublereal *mu) const
	Get the species electrochemical potentials. More...

virtual void	getPartialMolarIntEnergies (doublereal *ubar) const
	Return an array of partial molar internal energies 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...

doublereal	RT () const
	Return the Gas Constant multiplied by the current temperature. 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...

virtual void	setState (const AnyMap &state)
	Set the state using an AnyMap containing any combination of properties supported by the thermodynamic model. 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	equivalenceRatio () const
	Compute the equivalence ratio for the current mixture from available oxygen and required oxygen. 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

virtual void	initThermoFile (const std::string &inputFile, const std::string &id)

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...

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	setStateFromXML (const XML_Node &state)
	Set the initial state of the phase to the conditions specified in the state XML element. More...

virtual void	getdlnActCoeffdlnN_numderiv (const size_t ld, doublereal *const dlnActCoeffdlnN)

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...

virtual void	reportCSV (std::ofstream &csvFile) const
	returns a summary of the state of the phase to a comma separated file. 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...

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 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...

virtual bool	ready () const
	Returns a bool indicating whether the object is ready for use. More...

int	stateMFNumber () const
	Return the State Mole Fraction Number. More...

bool	caseSensitiveSpecies () const
	Returns `true` if case sensitive species names are enforced. More...

void	setCaseSensitiveSpecies (bool cflag=true)
	Set flag that determines whether case sensitive species are enforced in look-up operations, e.g. 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	id () const
	Return the string id for the phase. More...

void	setID (const std::string &id)
	Set the string id for the phase. 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	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...

doublereal	temperature () const
	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...

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 (i.e. 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...

Derivatives of Thermodynamic Variables needed for Applications
size_t	numBinaryInteractions_
	number of binary interaction expressions More...

vector_fp	m_HE_b_ij
	Enthalpy term for the binary mole fraction interaction of the excess Gibbs free energy expression. More...

vector_fp	m_HE_c_ij
	Enthalpy term for the ternary mole fraction interaction of the excess Gibbs free energy expression. More...

vector_fp	m_SE_b_ij
	Entropy term for the binary mole fraction interaction of the excess Gibbs free energy expression. More...

vector_fp	m_SE_c_ij
	Entropy term for the ternary mole fraction interaction of the excess Gibbs free energy expression. More...

vector_fp	m_VHE_b_ij
	Enthalpy term for the binary mole fraction interaction of the excess Gibbs free energy expression. More...

vector_fp	m_VHE_c_ij
	Enthalpy term for the ternary mole fraction interaction of the excess Gibbs free energy expression. More...

vector_fp	m_VSE_b_ij
	Entropy term for the binary mole fraction interaction of the excess Gibbs free energy expression. More...

vector_fp	m_VSE_c_ij
	Entropy term for the ternary mole fraction interaction of the excess Gibbs free energy expression. More...

std::vector< size_t >	m_pSpecies_A_ij
	vector of species indices representing species A in the interaction More...

std::vector< size_t >	m_pSpecies_B_ij
	vector of species indices representing species B in the interaction More...

int	formMargules_
	form of the Margules interaction expression More...

int	formTempModel_
	form of the temperature dependence of the Margules interaction expression 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_diag (doublereal *dlnActCoeffdlnN_diag) const
	Get the array of log species mole number derivatives of the log activity coefficients. 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...

void	readXMLBinarySpecies (XML_Node &xmlBinarySpecies)
	Process an XML node called "binaryNeutralSpeciesParameters". More...

void	initLengths ()
	Initialize lengths of local variables after all species have been identified. More...

void	s_update_lnActCoeff () const
	Update the activity coefficients. More...

void	s_update_dlnActCoeff_dT () const
	Update the derivative of the log of the activity coefficients wrt T. More...

void	s_update_dlnActCoeff_dlnX_diag () const
	Update the derivative of the log of the activity coefficients wrt log(mole fraction) More...

void	s_update_dlnActCoeff_dlnN_diag () const
	Update the derivative of the log of the activity coefficients wrt log(moles) - diagonal only. More...

void	s_update_dlnActCoeff_dlnN () const
	Update the derivative of the log of the activity coefficients wrt log(moles_m) More...

Additional Inherited Members
Protected Member Functions inherited from GibbsExcessVPSSTP
void	calcDensity ()
	Calculate the density of the mixture using the partial molar volumes and mole fractions as input. More...

virtual void	compositionChanged ()
	Apply changes to the state which are needed after the composition changes. More...

double	checkMFSum (const doublereal *const x) const
	utility routine to check mole fraction sum More...

Protected Member Functions inherited from VPStandardStateTP
virtual void	invalidateCache ()
	Invalidate any cached values which are normally updated only when a change in state is detected. More...

virtual void	_updateStandardStateThermo () const
	Updates the standard state thermodynamic functions at the current T and P of the solution. More...

const vector_fp &	Gibbs_RT_ref () const

Protected Member Functions inherited from ThermoPhase
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...

Protected Attributes inherited from GibbsExcessVPSSTP
vector_fp	moleFractions_
	Storage for the current values of the mole fractions of the species. More...

vector_fp	lnActCoeff_Scaled_
	Storage for the current values of the activity coefficients of the species. More...

vector_fp	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. More...

vector_fp	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. More...

vector_fp	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. More...

vector_fp	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. More...

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. 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...

Detailed Description

MargulesVPSSTP is a derived class of GibbsExcessVPSSTP that employs the Margules approximation for the excess Gibbs free energy.

MargulesVPSSTP derives from class GibbsExcessVPSSTP which is derived from VPStandardStateTP, and overloads the virtual methods defined there with ones that use expressions appropriate for the Margules Excess Gibbs free energy approximation.

The independent unknowns are pressure, temperature, and mass fraction.

Specification of Species Standard State Properties

All species are defined to have standard states that depend upon both the temperature and the pressure. The Margules approximation assumes symmetric standard states, where all of the standard state assume that the species are in pure component states at the temperature and pressure of the solution. I don't think it prevents, however, some species from being dilute in the solution.

Specification of Solution Thermodynamic Properties

The molar excess Gibbs free energy is given by the following formula which is a sum over interactions i. Each of the interactions are binary interactions involving two of the species in the phase, denoted, Ai and Bi. This is the generalization of the Margules formulation for a phase that has more than 2 species.

\[ G^E = \sum_i \left( H_{Ei} - T S_{Ei} \right) \]

\[ H^E_i = n X_{Ai} X_{Bi} \left( h_{o,i} + h_{1,i} X_{Bi} \right) \]

\[ S^E_i = n X_{Ai} X_{Bi} \left( s_{o,i} + s_{1,i} X_{Bi} \right) \]

where n is the total moles in the solution.

The activity of a species defined in the phase is given by an excess Gibbs free energy formulation.

\[ a_k = \gamma_k X_k \]

where

\[ R T \ln( \gamma_k )= \frac{d(n G^E)}{d(n_k)}\Bigg|_{n_i} \]

Taking the derivatives results in the following expression

\[ R T \ln( \gamma_k )= \sum_i \left( \left( \delta_{Ai,k} X_{Bi} + \delta_{Bi,k} X_{Ai} - X_{Ai} X_{Bi} \right) \left( g^E_{o,i} + g^E_{1,i} X_{Bi} \right) + \left( \delta_{Bi,k} - X_{Bi} \right) X_{Ai} X_{Bi} g^E_{1,i} \right) \]

where \( g^E_{o,i} = h_{o,i} - T s_{o,i} \) and \( g^E_{1,i} = h_{1,i} - T s_{1,i} \) and where \( X_k \) is the mole fraction of species k.

This object inherits from the class VPStandardStateTP. Therefore, the specification and calculation of all standard state and reference state values are handled at that level. Various functional forms for the standard state are permissible. The chemical potential for species k is equal to

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

The partial molar entropy for species k is given by

\[ \tilde{s}_k(T,P) = s^o_k(T,P) - R \ln( \gamma_k X_k ) - R T \frac{d \ln(\gamma_k) }{dT} \]

The partial molar enthalpy for species k is given by

\[ \tilde{h}_k(T,P) = h^o_k(T,P) - R T^2 \frac{d \ln(\gamma_k)}{dT} \]

The partial molar volume for species k is

\[ \tilde V_k(T,P) = V^o_k(T,P) + R T \frac{d \ln(\gamma_k) }{dP} \]

The partial molar Heat Capacity for species k is

\[ \tilde{C}_{p,k}(T,P) = C^o_{p,k}(T,P) - 2 R T \frac{d \ln( \gamma_k )}{dT} - R T^2 \frac{d^2 \ln(\gamma_k) }{{dT}^2} \]

%Application within Kinetics Managers

\( C^a_k\) are defined such that \( a_k = C^a_k / C^s_k, \) where \( C^s_k \) 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. The activity concentration, \( C^a_k \),is given by the following expression.

\[ C^a_k = C^s_k X_k = \frac{P}{R T} X_k \]

The standard concentration for species k is independent of k and equal to

\[ C^s_k = C^s = \frac{P}{R T} \]

For example, a bulk-phase binary gas reaction between species j and k, producing a new gas species l would have the following equation for its rate of progress variable, \( R^1 \), which has units of kmol m-3 s-1.

\[ R^1 = k^1 C_j^a C_k^a = k^1 (C^s a_j) (C^s a_k) \]

where

\[ C_j^a = C^s a_j \mbox{\quad and \quad} C_k^a = C^s a_k \]

\( C_j^a \) is the activity concentration of species j, and \( C_k^a \) is the activity concentration of species k. \( C^s \) is the standard concentration. \( a_j \) is the activity of species j which is equal to the mole fraction of j.

The reverse rate constant can then be obtained from the law of microscopic reversibility and the equilibrium expression for the system.

\[ \frac{a_j a_k}{ a_l} = K_a^{o,1} = \exp(\frac{\mu^o_l - \mu^o_j - \mu^o_k}{R T} ) \]

\( K_a^{o,1} \) is the dimensionless form of the equilibrium constant, associated with the pressure dependent standard states \( \mu^o_l(T,P) \) and their associated activities, \( a_l \), repeated here:

\[ \mu_l(T,P) = \mu^o_l(T, P) + R T \log(a_l) \]

We can switch over to expressing the equilibrium constant in terms of the reference state chemical potentials

\[ K_a^{o,1} = \exp(\frac{\mu^{ref}_l - \mu^{ref}_j - \mu^{ref}_k}{R T} ) * \frac{P_{ref}}{P} \]

The concentration equilibrium constant, \( K_c \), may be obtained by changing over to activity concentrations. When this is done:

\[ \frac{C^a_j C^a_k}{ C^a_l} = C^o K_a^{o,1} = K_c^1 = \exp(\frac{\mu^{ref}_l - \mu^{ref}_j - \mu^{ref}_k}{R T} ) * \frac{P_{ref}}{RT} \]

Kinetics managers will calculate the concentration equilibrium constant, \( K_c \), using the second and third part of the above expression as a definition for the concentration equilibrium constant.

For completeness, the pressure equilibrium constant may be obtained as well

\[ \frac{P_j P_k}{ P_l P_{ref}} = K_p^1 = \exp(\frac{\mu^{ref}_l - \mu^{ref}_j - \mu^{ref}_k}{R T} ) \]

\( K_p \) is the simplest form of the equilibrium constant for ideal gases. However, it isn't necessarily the simplest form of the equilibrium constant for other types of phases; \( K_c \) is used instead because it is completely general.

The reverse rate of progress may be written down as

\[ R^{-1} = k^{-1} C_l^a = k^{-1} (C^o a_l) \]

where we can use the concept of microscopic reversibility to write the reverse rate constant in terms of the forward rate constant and the concentration equilibrium constant, \( K_c \).

\[ k^{-1} = k^1 K^1_c \]

\(k^{-1} \) has units of s-1.

Definition at line 214 of file MargulesVPSSTP.h.

Constructor & Destructor Documentation

◆ MargulesVPSSTP() [1/2]

MargulesVPSSTP	(	const std::string &	inputFile,
		const std::string &	id = `""`
	)

Construct a MargulesVPSSTP object from an input file.

Parameters

inputFile	Name of the input file containing the phase definition
id	name (ID) of the phase in the input file. If empty, the first phase definition in the input file will be used.

Definition at line 28 of file MargulesVPSSTP.cpp.

References ThermoPhase::initThermoFile().

◆ MargulesVPSSTP() [2/2]

MargulesVPSSTP	(	XML_Node &	phaseRef,
		const std::string &	id = `""`
	)

Construct and initialize a MargulesVPSSTP ThermoPhase object directly from an XML database.

Parameters

phaseRef	XML phase node containing the description of the phase
id	id attribute containing the name of the phase. (default is the empty string)

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

Definition at line 36 of file MargulesVPSSTP.cpp.

References Cantera::importPhase().

Member Function Documentation

◆ type()

virtual std::string type ( ) const

inlinevirtual

String indicating the thermodynamic model implemented.

Usually corresponds to the name of the derived class, less any suffixes such as "Phase", TP", "VPSS", etc.

Reimplemented from ThermoPhase.

Definition at line 239 of file MargulesVPSSTP.h.

◆ enthalpy_mole()

doublereal enthalpy_mole ( ) const

virtual

Molar enthalpy. Units: J/kmol.

Reimplemented from ThermoPhase.

Definition at line 73 of file MargulesVPSSTP.cpp.

References MargulesVPSSTP::getPartialMolarEnthalpies(), GibbsExcessVPSSTP::moleFractions_, and Phase::nSpecies().

◆ entropy_mole()

doublereal entropy_mole ( ) const

virtual

Molar entropy. Units: J/kmol/K.

Reimplemented from ThermoPhase.

Definition at line 85 of file MargulesVPSSTP.cpp.

References MargulesVPSSTP::getPartialMolarEntropies(), GibbsExcessVPSSTP::moleFractions_, and Phase::nSpecies().

◆ cp_mole()

doublereal cp_mole ( ) const

virtual

Molar heat capacity at constant pressure. Units: J/kmol/K.

Reimplemented from ThermoPhase.

Definition at line 97 of file MargulesVPSSTP.cpp.

References MargulesVPSSTP::getPartialMolarCp(), GibbsExcessVPSSTP::moleFractions_, and Phase::nSpecies().

Referenced by MargulesVPSSTP::cv_mole().

◆ cv_mole()

doublereal cv_mole ( ) const

virtual

Molar heat capacity at constant volume. Units: J/kmol/K.

Reimplemented from ThermoPhase.

Definition at line 109 of file MargulesVPSSTP.cpp.

References MargulesVPSSTP::cp_mole(), and Cantera::GasConstant.

◆ getLnActivityCoefficients()

void getLnActivityCoefficients ( doublereal * lnac ) const

virtual

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

Parameters

lnac	Output vector of ln activity coefficients. Length: m_kk.

Reimplemented from ThermoPhase.

Definition at line 46 of file MargulesVPSSTP.cpp.

References GibbsExcessVPSSTP::lnActCoeff_Scaled_, Phase::m_kk, and MargulesVPSSTP::s_update_lnActCoeff().

◆ getChemPotentials()

void getChemPotentials ( doublereal * mu ) const

virtual

Get the species chemical potentials. Units: J/kmol.

This function returns a vector of chemical potentials of the species in solution at the current temperature, pressure and mole fraction of the solution.

Parameters

mu	Output vector of species chemical potentials. Length: m_kk. Units: J/kmol

Reimplemented from ThermoPhase.

Definition at line 59 of file MargulesVPSSTP.cpp.

References VPStandardStateTP::getStandardChemPotentials(), GibbsExcessVPSSTP::lnActCoeff_Scaled_, Phase::m_kk, GibbsExcessVPSSTP::moleFractions_, ThermoPhase::RT(), MargulesVPSSTP::s_update_lnActCoeff(), and Cantera::SmallNumber.

◆ getPartialMolarEnthalpies()

void getPartialMolarEnthalpies ( doublereal * hbar ) const

virtual

Returns an array of partial molar enthalpies for the species in the mixture.

Units (J/kmol)

For this phase, the partial molar enthalpies are equal to the standard state enthalpies modified by the derivative of the molality-based activity coefficient wrt temperature

\[ \bar h_k(T,P) = h^o_k(T,P) - R T^2 \frac{d \ln(\gamma_k)}{dT} \]

Parameters

hbar	Vector of returned partial molar enthalpies (length m_kk, units = J/kmol)

Reimplemented from ThermoPhase.

Definition at line 114 of file MargulesVPSSTP.cpp.

References GibbsExcessVPSSTP::dlnActCoeffdT_Scaled_, VPStandardStateTP::getEnthalpy_RT(), Phase::m_kk, ThermoPhase::RT(), MargulesVPSSTP::s_update_dlnActCoeff_dT(), MargulesVPSSTP::s_update_lnActCoeff(), and Phase::temperature().

Referenced by MargulesVPSSTP::enthalpy_mole().

◆ getPartialMolarEntropies()

void getPartialMolarEntropies ( doublereal * sbar ) const

virtual

Returns an array of partial molar entropies for the species in the mixture.

Units (J/kmol)

For this phase, the partial molar enthalpies are equal to the standard state enthalpies modified by the derivative of the activity coefficient wrt temperature

\[ \bar s_k(T,P) = s^o_k(T,P) - R T^2 \frac{d \ln(\gamma_k)}{dT} - R \ln( \gamma_k X_k) - R T \frac{d \ln(\gamma_k) }{dT} \]

Parameters

sbar	Vector of returned partial molar entropies (length m_kk, units = J/kmol/K)

Reimplemented from ThermoPhase.

Definition at line 153 of file MargulesVPSSTP.cpp.

References VPStandardStateTP::getEntropy_R().

Referenced by MargulesVPSSTP::entropy_mole().

◆ getPartialMolarCp()

void getPartialMolarCp ( doublereal * cpbar ) const

virtual

Returns an array of partial molar entropies for the species in the mixture.

Units (J/kmol)

For this phase, the partial molar enthalpies are equal to the standard state enthalpies modified by the derivative of the activity coefficient wrt temperature

\[ ??????????????? \bar s_k(T,P) = s^o_k(T,P) - R T^2 \frac{d \ln(\gamma_k)}{dT} - R \ln( \gamma_k X_k) - R T \frac{d \ln(\gamma_k) }{dT} ??????????????? \]

Parameters

cpbar Vector of returned partial molar heat capacities (length m_kk, units = J/kmol/K)

Reimplemented from ThermoPhase.

Definition at line 133 of file MargulesVPSSTP.cpp.

References VPStandardStateTP::getCp_R().

Referenced by MargulesVPSSTP::cp_mole().

◆ getPartialMolarVolumes()

void getPartialMolarVolumes ( doublereal * vbar ) const

virtual

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

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

Reimplemented from GibbsExcessVPSSTP.

Definition at line 175 of file MargulesVPSSTP.cpp.

◆ getd2lnActCoeffdT2()

void getd2lnActCoeffdT2 ( doublereal * d2lnActCoeffdT2 ) const

virtual

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

units = 1/Kelvin

Parameters

d2lnActCoeffdT2 Output vector of temperature 2nd derivatives of the log Activity Coefficients. length = m_kk

Definition at line 362 of file MargulesVPSSTP.cpp.

References GibbsExcessVPSSTP::d2lnActCoeffdT2_Scaled_, Phase::m_kk, and MargulesVPSSTP::s_update_dlnActCoeff_dT().

◆ getdlnActCoeffdT()

void getdlnActCoeffdT ( doublereal * dlnActCoeffdT ) const

virtual

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

This function is virtual, and first appears in GibbsExcessVPSSTP.

units = 1/Kelvin

Parameters

dlnActCoeffdT Output vector of temperature derivatives of the log Activity Coefficients. length = m_kk

Reimplemented from GibbsExcessVPSSTP.

Definition at line 354 of file MargulesVPSSTP.cpp.

References GibbsExcessVPSSTP::dlnActCoeffdT_Scaled_, Phase::m_kk, and MargulesVPSSTP::s_update_dlnActCoeff_dT().

◆ 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.

Definition at line 200 of file MargulesVPSSTP.cpp.

References MargulesVPSSTP::addBinaryInteraction(), AnyMap::hasKey(), MargulesVPSSTP::initLengths(), VPStandardStateTP::initThermo(), ThermoPhase::m_input, and Phase::species().

◆ initThermoXML()

void initThermoXML	(	XML_Node &	phaseNode,
		const std::string &	id
	)

virtual

Import and initialize a ThermoPhase object using an XML tree.

Here we read extra information about the XML description of a phase. Regular information about elements and species and their reference state thermodynamic information have already been read at this point. For example, we do not need to call this function for ideal gas equations of state. This function is called from importPhase() after the elements and the species are initialized with default ideal solution level data.

The default implementation in ThermoPhase calls the virtual function initThermo() and then sets the "state" of the phase by looking for an XML element named "state", and then interpreting its contents by calling the virtual function setStateFromXML().

Parameters

phaseNode	This object must be the phase node of a complete XML tree description of the phase, including all of the species data. In other words while "phase" must point to an XML phase object, it must have sibling nodes "speciesData" that describe the species in the phase.
id	ID of the phase. If nonnull, a check is done to see if phaseNode is pointing to the phase with the correct id.

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

Reimplemented from ThermoPhase.

Definition at line 231 of file MargulesVPSSTP.cpp.

References Cantera::caseInsensitiveEquals(), XML_Node::child(), XML_Node::hasChild(), XML_Node::id(), ThermoPhase::initThermoXML(), XML_Node::name(), XML_Node::nChildren(), and MargulesVPSSTP::readXMLBinarySpecies().

◆ addBinaryInteraction()

void addBinaryInteraction	(	const std::string &	speciesA,
		const std::string &	speciesB,
		double	h0,
		double	h1,
		double	s0,
		double	s1,
		double	vh0,
		double	vh1,
		double	vs0,
		double	vs1
	)

Add a binary species interaction with the specified parameters.

Parameters

speciesA	name of the first species
speciesB	name of the second species
h0	first excess enthalpy coefficient [J/kmol]
h1	second excess enthalpy coefficient [J/kmol]
s0	first excess entropy coefficient [J/kmol/K]
s1	second excess entropy coefficient [J/kmol/K]
vh0	first enthalpy coefficient for excess volume [m^3/kmol]
vh1	second enthalpy coefficient for excess volume [m^3/kmol]
vs0	first entropy coefficient for excess volume [m^3/kmol/K]
vs1	second entropy coefficient for excess volume [m^3/kmol/K]

Definition at line 277 of file MargulesVPSSTP.cpp.

Referenced by MargulesVPSSTP::initThermo().

◆ getdlnActCoeffds()

void getdlnActCoeffds	(	const doublereal	dTds,
		const doublereal *const	dXds,
		doublereal *	dlnActCoeffds
	)		const

virtual

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.

Parameters

dTds	Input of temperature change along the path
dXds	Input vector of changes in mole fraction along the path. length = m_kk Along the path length it must be the case that the mole fractions sum to one.
dlnActCoeffds	Output vector of the directional derivatives of the log Activity Coefficients along the path. length = m_kk units are 1/units(s). if s is a physical coordinate then the units are 1/m.

Reimplemented from ThermoPhase.

Definition at line 370 of file MargulesVPSSTP.cpp.

◆ getdlnActCoeffdlnX_diag()

void getdlnActCoeffdlnX_diag ( doublereal * dlnActCoeffdlnX_diag ) const

virtual

Get the array of ln mole fraction derivatives of the log activity coefficients - diagonal component only.

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 mole fraction variable that represents the standard state. This quantity is to be used in conjunction with derivatives of that mole fraction variable when the derivative of the chemical potential is taken.

units = dimensionless

Parameters

dlnActCoeffdlnX_diag Output vector of derivatives of the log Activity Coefficients wrt the mole fractions. length = m_kk

Reimplemented from ThermoPhase.

Definition at line 498 of file MargulesVPSSTP.cpp.

References GibbsExcessVPSSTP::dlnActCoeffdlnX_diag_, Phase::m_kk, and MargulesVPSSTP::s_update_dlnActCoeff_dlnX_diag().

◆ getdlnActCoeffdlnN_diag()

void getdlnActCoeffdlnN_diag ( doublereal * dlnActCoeffdlnN_diag ) const

virtual

Get the array of log species mole number derivatives of the log activity coefficients.

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 (i.e. moles) that represents the standard state. This quantity is to be used in conjunction with derivatives of that species mole number variable when the derivative of the chemical potential is taken.

units = dimensionless

Parameters

dlnActCoeffdlnN_diag Output vector of derivatives of the log Activity Coefficients. length = m_kk

Reimplemented from VPStandardStateTP.

Definition at line 490 of file MargulesVPSSTP.cpp.

References GibbsExcessVPSSTP::dlnActCoeffdlnN_diag_, Phase::m_kk, and MargulesVPSSTP::s_update_dlnActCoeff_dlnN_diag().

◆ getdlnActCoeffdlnN()

void getdlnActCoeffdlnN	(	const size_t	ld,
		doublereal *const	dlnActCoeffdlnN
	)

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 GibbsExcessVPSSTP.

Definition at line 506 of file MargulesVPSSTP.cpp.

References GibbsExcessVPSSTP::dlnActCoeffdlnN_, Phase::m_kk, and MargulesVPSSTP::s_update_dlnActCoeff_dlnN().

◆ readXMLBinarySpecies()

void readXMLBinarySpecies ( XML_Node & xmlBinarySpecies )

private

Process an XML node called "binaryNeutralSpeciesParameters".

This node contains all of the parameters necessary to describe the Margules model for a particular binary interaction. This function reads the XML file and writes the coefficients it finds to an internal data structures.

Parameters

xmlBinarySpecies Reference to the XML_Node named "binaryNeutralSpeciesParameters" containing the binary interaction

Definition at line 517 of file MargulesVPSSTP.cpp.

References XML_Node::attrib(), and XML_Node::name().

Referenced by MargulesVPSSTP::initThermoXML().

◆ initLengths()

void initLengths ( )

private

Initialize lengths of local variables after all species have been identified.

Definition at line 226 of file MargulesVPSSTP.cpp.

References GibbsExcessVPSSTP::dlnActCoeffdlnN_, Phase::m_kk, and Array2D::resize().

Referenced by MargulesVPSSTP::initThermo().

◆ s_update_lnActCoeff()

void s_update_lnActCoeff ( ) const

private

Update the activity coefficients.

This function will be called to update the internally stored natural logarithm of the activity coefficients

Definition at line 303 of file MargulesVPSSTP.cpp.

Referenced by MargulesVPSSTP::getChemPotentials(), MargulesVPSSTP::getLnActivityCoefficients(), and MargulesVPSSTP::getPartialMolarEnthalpies().

◆ s_update_dlnActCoeff_dT()

void s_update_dlnActCoeff_dT ( ) const

private

Update the derivative of the log of the activity coefficients wrt T.

This function will be called to update the internally stored derivative of the natural logarithm of the activity coefficients wrt temperature.

Definition at line 325 of file MargulesVPSSTP.cpp.

References GibbsExcessVPSSTP::d2lnActCoeffdT2_Scaled_, GibbsExcessVPSSTP::dlnActCoeffdT_Scaled_, Cantera::GasConstant, MargulesVPSSTP::m_HE_b_ij, MargulesVPSSTP::m_HE_c_ij, Phase::m_kk, MargulesVPSSTP::m_pSpecies_A_ij, MargulesVPSSTP::m_pSpecies_B_ij, GibbsExcessVPSSTP::moleFractions_, MargulesVPSSTP::numBinaryInteractions_, and Phase::temperature().

Referenced by MargulesVPSSTP::getd2lnActCoeffdT2(), MargulesVPSSTP::getdlnActCoeffdT(), and MargulesVPSSTP::getPartialMolarEnthalpies().

◆ s_update_dlnActCoeff_dlnX_diag()

void s_update_dlnActCoeff_dlnX_diag ( ) const

private

Update the derivative of the log of the activity coefficients wrt log(mole fraction)

This function will be called to update the internally stored derivative of the natural logarithm of the activity coefficients wrt logarithm of the mole fractions.

Definition at line 470 of file MargulesVPSSTP.cpp.

Referenced by MargulesVPSSTP::getdlnActCoeffdlnX_diag().

◆ s_update_dlnActCoeff_dlnN_diag()

void s_update_dlnActCoeff_dlnN_diag ( ) const

private

Update the derivative of the log of the activity coefficients wrt log(moles) - diagonal only.

This function will be called to update the internally stored diagonal entries for the derivative of the natural logarithm of the activity coefficients wrt logarithm of the moles.

Definition at line 399 of file MargulesVPSSTP.cpp.

Referenced by MargulesVPSSTP::getdlnActCoeffdlnN_diag().

◆ s_update_dlnActCoeff_dlnN()

void s_update_dlnActCoeff_dlnN ( ) const

private

Update the derivative of the log of the activity coefficients wrt log(moles_m)

This function will be called to update the internally stored derivative of the natural logarithm of the activity coefficients wrt logarithm of the mole number of species

Definition at line 431 of file MargulesVPSSTP.cpp.

Referenced by MargulesVPSSTP::getdlnActCoeffdlnN().

Member Data Documentation

◆ numBinaryInteractions_

size_t numBinaryInteractions_

protected

number of binary interaction expressions

Definition at line 442 of file MargulesVPSSTP.h.

Referenced by MargulesVPSSTP::s_update_dlnActCoeff_dT().

◆ m_HE_b_ij

vector_fp m_HE_b_ij

mutableprotected

Enthalpy term for the binary mole fraction interaction of the excess Gibbs free energy expression.

Definition at line 446 of file MargulesVPSSTP.h.

Referenced by MargulesVPSSTP::s_update_dlnActCoeff_dT().

◆ m_HE_c_ij

vector_fp m_HE_c_ij

mutableprotected

Enthalpy term for the ternary mole fraction interaction of the excess Gibbs free energy expression.

Definition at line 450 of file MargulesVPSSTP.h.

Referenced by MargulesVPSSTP::s_update_dlnActCoeff_dT().

◆ m_SE_b_ij

vector_fp m_SE_b_ij

mutableprotected

Entropy term for the binary mole fraction interaction of the excess Gibbs free energy expression.

Definition at line 454 of file MargulesVPSSTP.h.

◆ m_SE_c_ij

vector_fp m_SE_c_ij

mutableprotected

Entropy term for the ternary mole fraction interaction of the excess Gibbs free energy expression.

Definition at line 458 of file MargulesVPSSTP.h.

◆ m_VHE_b_ij

vector_fp m_VHE_b_ij

mutableprotected

Enthalpy term for the binary mole fraction interaction of the excess Gibbs free energy expression.

Definition at line 462 of file MargulesVPSSTP.h.

◆ m_VHE_c_ij

vector_fp m_VHE_c_ij

mutableprotected

Enthalpy term for the ternary mole fraction interaction of the excess Gibbs free energy expression.

Definition at line 466 of file MargulesVPSSTP.h.

◆ m_VSE_b_ij

vector_fp m_VSE_b_ij

mutableprotected

Entropy term for the binary mole fraction interaction of the excess Gibbs free energy expression.

Definition at line 470 of file MargulesVPSSTP.h.

◆ m_VSE_c_ij

vector_fp m_VSE_c_ij

mutableprotected

Entropy term for the ternary mole fraction interaction of the excess Gibbs free energy expression.

Definition at line 474 of file MargulesVPSSTP.h.

◆ m_pSpecies_A_ij

std::vector<size_t> m_pSpecies_A_ij

protected

vector of species indices representing species A in the interaction

Each Margules excess Gibbs free energy term involves two species, A and B. This vector identifies species A.

Definition at line 481 of file MargulesVPSSTP.h.

Referenced by MargulesVPSSTP::s_update_dlnActCoeff_dT().

◆ m_pSpecies_B_ij

std::vector<size_t> m_pSpecies_B_ij

protected

vector of species indices representing species B in the interaction

Each Margules excess Gibbs free energy term involves two species, A and B. This vector identifies species B.

Definition at line 488 of file MargulesVPSSTP.h.

Referenced by MargulesVPSSTP::s_update_dlnActCoeff_dT().

◆ formMargules_

int formMargules_

protected

form of the Margules interaction expression

Currently there is only one form.

Definition at line 494 of file MargulesVPSSTP.h.

◆ formTempModel_

int formTempModel_

protected

form of the temperature dependence of the Margules interaction expression

Currently there is only one form -> constant wrt temperature.

Definition at line 500 of file MargulesVPSSTP.h.

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

Public Member Functions

Derivatives of Thermodynamic Variables needed for Applications

Additional Inherited Members

Detailed Description

Specification of Species Standard State Properties

Specification of Solution Thermodynamic Properties

%Application within Kinetics Managers

Constructor & Destructor Documentation

◆ MargulesVPSSTP() [1/2]

◆ MargulesVPSSTP() [2/2]

Member Function Documentation

◆ type()

◆ enthalpy_mole()

◆ entropy_mole()

◆ cp_mole()

◆ cv_mole()

◆ getLnActivityCoefficients()

◆ getChemPotentials()

◆ getPartialMolarEnthalpies()

◆ getPartialMolarEntropies()

◆ getPartialMolarCp()

◆ getPartialMolarVolumes()

◆ getd2lnActCoeffdT2()

◆ getdlnActCoeffdT()

◆ initThermo()

◆ initThermoXML()

◆ addBinaryInteraction()

◆ getdlnActCoeffds()

◆ getdlnActCoeffdlnX_diag()

◆ getdlnActCoeffdlnN_diag()

◆ getdlnActCoeffdlnN()

◆ readXMLBinarySpecies()

◆ initLengths()

◆ s_update_lnActCoeff()

◆ s_update_dlnActCoeff_dT()

◆ s_update_dlnActCoeff_dlnX_diag()

◆ s_update_dlnActCoeff_dlnN_diag()

◆ s_update_dlnActCoeff_dlnN()

Member Data Documentation

◆ numBinaryInteractions_

◆ m_HE_b_ij

◆ m_HE_c_ij

◆ m_SE_b_ij

◆ m_SE_c_ij

◆ m_VHE_b_ij

◆ m_VHE_c_ij

◆ m_VSE_b_ij

◆ m_VSE_c_ij

◆ m_pSpecies_A_ij

◆ m_pSpecies_B_ij

◆ formMargules_

◆ formTempModel_