This is the main structure used to hold the internal data used in vcs_solve_TP(), and to solve TP systems. More...

#include <vcs_solve.h>

Detailed Description

This is the main structure used to hold the internal data used in vcs_solve_TP(), and to solve TP systems.

The indices of information in this structure may change when the species basis changes or when phases pop in and out of existence. Both of these operations change the species ordering.

Definition at line 44 of file vcs_solve.h.

Public Member Functions
	VCS_SOLVE (MultiPhase *mphase, int printLvl=0)
	Initialize the sizes within the VCS_SOLVE object. More...

int	vcs (int ipr, int ip1, int maxit)
	Solve an equilibrium problem. More...

int	vcs_solve_TP (int print_lvl, int printDetails, int maxit)
	Main routine that solves for equilibrium at constant T and P using a variant of the VCS method. More...

void	vcs_reinsert_deleted (size_t kspec)
	We make decisions on the initial mole number, and major-minor status here. More...

int	vcs_basopt (const bool doJustComponents, double aw[], double sa[], double sm[], double ss[], double test, bool *const usedZeroedSpecies)
	Choose the optimum species basis for the calculations. More...

size_t	vcs_basisOptMax (const double *const molNum, const size_t j, const size_t n)
	Choose a species to test for the next component. More...

int	vcs_species_type (const size_t kspec) const
	Evaluate the species category for the indicated species. More...

bool	vcs_evaluate_speciesType ()
	This routine evaluates the species type for all species. More...

void	vcs_dfe (const int stateCalc, const int ll, const size_t lbot, const size_t ltop)
	Calculate the dimensionless chemical potentials of all species or of certain groups of species, at a fixed temperature and pressure. More...

void	vcs_updateVP (const int stateCalc)
	This routine uploads the state of the system into all of the vcs_VolumePhase objects in the current problem. More...

bool	vcs_popPhasePossible (const size_t iphasePop) const
	Utility function that evaluates whether a phase can be popped into existence. More...

size_t	vcs_popPhaseID (vector< size_t > &phasePopPhaseIDs)
	Decision as to whether a phase pops back into existence. More...

int	vcs_popPhaseRxnStepSizes (const size_t iphasePop)
	Calculates the deltas of the reactions due to phases popping into existence. More...

size_t	vcs_RxnStepSizes (int &forceComponentCalc, size_t &kSpecial)
	Calculates formation reaction step sizes. More...

double	vcs_tmoles ()
	Calculates the total number of moles of species in all phases. More...

void	check_tmoles () const

void	vcs_deltag (const int L, const bool doDeleted, const int vcsState, const bool alterZeroedPhases=true)
	This subroutine calculates reaction free energy changes for all noncomponent formation reactions. More...

void	vcs_printDeltaG (const int stateCalc)

void	vcs_switch_pos (const bool ifunc, const size_t k1, const size_t k2)
	Swaps the indices for all of the global data for two species, k1 and k2. More...

double	vcs_phaseStabilityTest (const size_t iph)
	Main program to test whether a deleted phase should be brought back into existence. More...

int	vcs_TP (int ipr, int ip1, int maxit, double T, double pres)
	Solve an equilibrium problem at a particular fixed temperature and pressure. More...

int	vcs_evalSS_TP (int ipr, int ip1, double Temp, double pres)
	Evaluate the standard state free energies at the current temperature and pressure. More...

void	vcs_fePrep_TP ()
	Initialize the chemical potential of single species phases. More...

double	vcs_VolTotal (const double tkelvin, const double pres, const double w[], double volPM[])
	Calculation of the total volume and the partial molar volumes. More...

int	vcs_prep (int printLvl)
	This routine is mostly concerned with changing the private data to be consistent with what's needed for solution. More...

int	vcs_elem_rearrange (double const aw, double const sa, double const sm, double const ss)
	Rearrange the constraint equations represented by the Formula Matrix so that the operational ones are in the front. More...

void	vcs_switch_elem_pos (size_t ipos, size_t jpos)
	Swaps the indices for all of the global data for two elements, ipos and jpos. More...

double	vcs_Hessian_diag_adj (size_t irxn, double hessianDiag_Ideal)
	Calculates the diagonal contribution to the Hessian due to the dependence of the activity coefficients on the mole numbers. More...

double	vcs_Hessian_actCoeff_diag (size_t irxn)
	Calculates the diagonal contribution to the Hessian due to the dependence of the activity coefficients on the mole numbers. More...

void	vcs_CalcLnActCoeffJac (const double *const moleSpeciesVCS)
	Recalculate all of the activity coefficients in all of the phases based on input mole numbers. More...

int	vcs_report (int iconv)
	Print out a report on the state of the equilibrium problem to standard output. More...

void	vcs_elab ()
	Computes the current elemental abundances vector. More...

bool	vcs_elabcheck (int ibound)
	Checks to see if the element abundances are in compliance. More...

void	vcs_elabPhase (size_t iphase, double *const elemAbundPhase)
	Computes the elemental abundances vector for a single phase, elemAbundPhase[], and returns it through the argument list. More...

int	vcs_elcorr (double aa[], double x[])
	This subroutine corrects for element abundances. More...

int	vcs_inest_TP ()
	Create an initial estimate of the solution to the thermodynamic equilibrium problem. More...

int	vcs_setMolesLinProg ()
	Estimate the initial mole numbers by constrained linear programming. More...

double	vcs_Total_Gibbs (double w, double fe, double *tPhMoles)
	Calculate the total dimensionless Gibbs free energy. More...

double	vcs_GibbsPhase (size_t iphase, const double const w, const double const fe)
	Calculate the total dimensionless Gibbs free energy of a single phase. More...

void	vcs_prob_update ()
	Transfer the results of the equilibrium calculation back from VCS_SOLVE. More...

void	vcs_prob_specifyFully ()
	Fully specify the problem to be solved. More...

void	prob_report (int print_lvl)
	Print out the problem specification in all generality as it currently exists in the VCS_SOLVE object. More...

void	addPhaseElements (vcs_VolPhase *volPhase)
	Add elements to the local element list. More...

size_t	addOnePhaseSpecies (vcs_VolPhase *volPhase, size_t k, size_t kT)
	This routines adds entries for the formula matrix for one species. More...

size_t	addElement (const char *elNameNew, int elType, int elactive)
	This routine resizes the number of elements in the VCS_SOLVE object by adding a new element to the end of the element list. More...

void	reportCSV (const string &reportFile)

Static Public Member Functions
static void	disableTiming ()
	Disable printing of timing information. More...

Public Attributes
int	m_printLvl
	Print level for print routines. More...

MultiPhase *	m_mix

size_t	m_nsp
	Total number of species in the problems. More...

size_t	m_nelem = 0
	Number of element constraints in the problem. More...

size_t	m_numComponents = 0
	Number of components calculated for the problem. More...

size_t	m_numRxnTot = 0
	Total number of non-component species in the problem. More...

size_t	m_numSpeciesRdc
	Current number of species in the problems. More...

size_t	m_numRxnRdc = 0
	Current number of non-component species in the problem. More...

size_t	m_numRxnMinorZeroed = 0
	Number of active species which are currently either treated as minor species. More...

size_t	m_numPhases
	Number of Phases in the problem. More...

Array2D	m_formulaMatrix
	Formula matrix for the problem. More...

Array2D	m_stoichCoeffRxnMatrix
	Stoichiometric coefficient matrix for the reaction mechanism expressed in Reduced Canonical Form. More...

vector< double >	m_scSize
	Absolute size of the stoichiometric coefficients. More...

vector< double >	m_spSize
	total size of the species More...

vector< double >	m_SSfeSpecies
	Standard state chemical potentials for species K at the current temperature and pressure. More...

vector< double >	m_feSpecies_old
	Free energy vector from the start of the current iteration. More...

vector< double >	m_feSpecies_new
	Dimensionless new free energy for all the species in the mechanism at the new tentative T, P, and mole numbers. More...

int	m_doEstimateEquil = -1
	Setting for whether to do an initial estimate. More...

vector< double >	m_molNumSpecies_old
	Total moles of the species. More...

vector< int >	m_speciesUnknownType
	Specifies the species unknown type. More...

Array2D	m_deltaMolNumPhase
	Change in the number of moles of phase, iphase, due to the noncomponent formation reaction, irxn, for species, k: More...

Array2D	m_phaseParticipation
	This is 1 if the phase, iphase, participates in the formation reaction irxn, and zero otherwise. More...

vector< double >	m_phasePhi
	electric potential of the iph phase More...

vector< double >	m_molNumSpecies_new
	Tentative value of the mole number vector. More...

vector< double >	m_deltaGRxn_new
	Delta G(irxn) for the noncomponent species in the mechanism. More...

vector< double >	m_deltaGRxn_old
	Last deltag[irxn] from the previous step. More...

vector< double >	m_deltaGRxn_Deficient
	Last deltag[irxn] from the previous step with additions for possible births of zeroed phases. More...

vector< double >	m_deltaGRxn_tmp
	Temporary vector of Rxn DeltaG's. More...

vector< double >	m_deltaMolNumSpecies
	Reaction Adjustments for each species during the current step. More...

vector< double >	m_elemAbundances
	Element abundances vector. More...

vector< double >	m_elemAbundancesGoal
	Element abundances vector Goals. More...

double	m_totalMolNum = 0.0
	Total number of kmoles in all phases. More...

vector< double >	m_tPhaseMoles_old
	Total kmols of species in each phase. More...

vector< double >	m_tPhaseMoles_new
	total kmols of species in each phase in the tentative soln vector More...

vector< double >	m_TmpPhase
	Temporary vector of length NPhase. More...

vector< double >	m_TmpPhase2
	Temporary vector of length NPhase. More...

vector< double >	m_deltaPhaseMoles
	Change in the total moles in each phase. More...

double	m_temperature
	Temperature (Kelvin) More...

double	m_pressurePA
	Pressure. More...

vector< double >	TPhInertMoles
	Total kmoles of inert to add to each phase. More...

double	m_tolmaj = 1e-8
	Tolerance requirement for major species. More...

double	m_tolmin = 1e-6
	Tolerance requirements for minor species. More...

double	m_tolmaj2 = 1e-10
	Below this, major species aren't refined any more. More...

double	m_tolmin2 = 1e-8
	Below this, minor species aren't refined any more. More...

vector< size_t >	m_speciesMapIndex
	Index vector that keeps track of the species vector rearrangement. More...

vector< size_t >	m_speciesLocalPhaseIndex
	Index that keeps track of the index of the species within the local phase. More...

vector< size_t >	m_elementMapIndex
	Index vector that keeps track of the rearrangement of the elements. More...

vector< size_t >	m_indexRxnToSpecies
	Mapping between the species index for noncomponent species and the full species index. More...

vector< int >	m_speciesStatus
	Major -Minor status vector for the species in the problem. More...

vector< size_t >	m_phaseID
	Mapping from the species number to the phase number. More...

vector< char >	m_SSPhase
	Boolean indicating whether a species belongs to a single-species phase. More...

vector< string >	m_speciesName
	Species string name for the kth species. More...

vector< string >	m_elementName
	Vector of strings containing the element names. More...

vector< int >	m_elType
	Type of the element constraint. More...

vector< int >	m_elementActive
	Specifies whether an element constraint is active. More...

vector< unique_ptr< vcs_VolPhase > >	m_VolPhaseList
	Array of Phase Structures. Length = number of phases. More...

vector< int >	m_actConventionSpecies
	specifies the activity convention of the phase containing the species More...

vector< int >	m_phaseActConvention
	specifies the activity convention of the phase. More...

vector< double >	m_lnMnaughtSpecies
	specifies the ln(Mnaught) used to calculate the chemical potentials More...

vector< double >	m_actCoeffSpecies_new
	Molar-based Activity Coefficients for Species. More...

vector< double >	m_actCoeffSpecies_old
	Molar-based Activity Coefficients for Species based on old mole numbers. More...

Array2D	m_np_dLnActCoeffdMolNum
	Change in the log of the activity coefficient with respect to the mole number multiplied by the phase mole number. More...

vector< double >	m_wtSpecies
	Molecular weight of each species. More...

vector< double >	m_chargeSpecies
	Charge of each species. Length = number of species. More...

vector< vector< size_t > >	phasePopProblemLists_

vector< unique_ptr< VCS_SPECIES_THERMO > >	m_speciesThermoList
	Vector of pointers to thermo structures which identify the model and parameters for evaluating the thermodynamic functions for that particular species. More...

int	m_useActCoeffJac = 0
	Choice of Hessians. More...

double	m_totalVol
	Total volume of all phases. Units are m^3. More...

vector< double >	m_PMVolumeSpecies
	Partial molar volumes of the species. More...

double	m_Faraday_dim
	dimensionless value of Faraday's constant, F / RT (1/volt) More...

VCS_COUNTERS *	m_VCount = nullptr
	Timing and iteration counters for the vcs object. More...

int	m_debug_print_lvl = 0
	Debug printing lvl. More...

int	m_timing_print_lvl = 1
	printing level of timing information More...

Private Member Functions
int	vcs_zero_species (const size_t kspec)
	Zero out the concentration of a species. More...

int	vcs_delete_species (const size_t kspec)
	Change a single species from active to inactive status. More...

bool	vcs_delete_multiphase (const size_t iph)
	This routine handles the bookkeeping involved with the deletion of multiphase phases from the problem. More...

int	delta_species (const size_t kspec, double *const delta_ptr)
	Change the concentration of a species by delta moles. More...

size_t	vcs_add_all_deleted ()
	Provide an estimate for the deleted species in phases that are not zeroed out. More...

int	vcs_recheck_deleted ()
	Recheck deleted species in multispecies phases. More...

double	vcs_minor_alt_calc (size_t kspec, size_t irxn, bool do_delete, char ANOTE=0) const
	Minor species alternative calculation. More...

bool	vcs_globStepDamp ()
	This routine optimizes the minimization of the total Gibbs free energy by making sure the slope of the following functional stays negative: More...

double	l2normdg (double dg[]) const
	Calculate the norm of a deltaGibbs free energy vector. More...

void	checkDelta1 (double const ds, double const delTPhMoles, size_t kspec)

void	vcs_inest (double const aw, double const sa, double const sm, double const ss, double test)
	Estimate equilibrium compositions. More...

void	vcs_SSPhase ()
	Calculate the status of single species phases. More...

void	vcs_delete_memory ()
	Delete memory that isn't just resizable STL containers. More...

void	vcs_counters_init (int ifunc)
	Initialize the internal counters. More...

void	vcs_TCounters_report (int timing_print_lvl=1)
	Create a report on the plog file containing timing and its information. More...

void	vcs_setFlagsVolPhases (const bool upToDate, const int stateCalc)

void	vcs_setFlagsVolPhase (const size_t iph, const bool upToDate, const int stateCalc)

void	vcs_updateMolNumVolPhases (const int stateCalc)
	Update all underlying vcs_VolPhase objects. More...

int	solve_tp_component_calc (bool &allMinorZeroedSpecies)

void	solve_tp_inner (size_t &iti, size_t &it1, bool &uptodate_minors, bool &allMinorZeroedSpecies, int &forceComponentCalc, int &stage, bool printDetails, char *ANOTE)

void	solve_tp_equilib_check (bool &allMinorZeroedSpecies, bool &uptodate_minors, bool &giveUpOnElemAbund, int &solveFail, size_t &iti, size_t &it1, int maxit, int &stage, bool &lec)

void	solve_tp_elem_abund_check (size_t &iti, int &stage, bool &lec, bool &giveUpOnElemAbund, int &finalElemAbundAttempts, int &rangeErrorFound)

Private Attributes
vector< double >	m_sm

vector< double >	m_ss

vector< double >	m_sa

vector< double >	m_aw

vector< double >	m_wx

Friends
class	vcs_phaseStabilitySolve

Constructor & Destructor Documentation

◆ VCS_SOLVE()

VCS_SOLVE	(	MultiPhase *	mphase,
		int	printLvl = `0`
	)

Initialize the sizes within the VCS_SOLVE object.

This resizes all of the internal arrays within the object.

Definition at line 44 of file vcs_solve.cpp.

Member Function Documentation

◆ vcs()

int vcs	(	int	ipr,
		int	ip1,
		int	maxit
	)

Solve an equilibrium problem.

This is the main interface routine to the equilibrium solver

Parameters

ipr	Printing of results ipr = 1 -> Print problem statement and final results to standard output 0 -> don't report on anything
ip1	Printing of intermediate results IP1 = 1 -> Print intermediate results.
maxit	Maximum number of iterations for the algorithm

Returns: nonzero value: failure to solve the problem at hand. zero : success

Definition at line 476 of file vcs_solve.cpp.

◆ vcs_solve_TP()

int vcs_solve_TP	(	int	print_lvl,
		int	printDetails,
		int	maxit
	)

Main routine that solves for equilibrium at constant T and P using a variant of the VCS method.

This is the main routine that solves for equilibrium at constant T and P using a variant of the VCS method. Nonideal phases can be accommodated as well.

Any number of single-species phases and multi-species phases can be handled by the present version.

Parameters

print_lvl	1 -> Print results to standard output; 0 -> don't report on anything
printDetails	1 -> Print intermediate results.
maxit	Maximum number of iterations for the algorithm

Returns

0 = Equilibrium Achieved
1 = Range space error encountered. The element abundance criteria are only partially satisfied. Specifically, the first NC= (number of components) conditions are satisfied. However, the full NE (number of elements) conditions are not satisfied. The equilibrium condition is returned.
-1 = Maximum number of iterations is exceeded. Convergence was not found.

Definition at line 49 of file vcs_solve_TP.cpp.

◆ vcs_reinsert_deleted()

void vcs_reinsert_deleted ( size_t kspec )

We make decisions on the initial mole number, and major-minor status here.

We also fix up the total moles in a phase.

irxn = id of the noncomponent species formation reaction for the species to be added in.

The algorithm proceeds to implement these decisions in the previous position of the species. Then, vcs_switch_pos is called to move the species into the last active species slot, incrementing the number of active species at the same time.

This routine is responsible for the global data manipulation only.

Definition at line 1572 of file vcs_solve_TP.cpp.

◆ vcs_basopt()

int vcs_basopt	(	const bool	doJustComponents,
		double	aw[],
		double	sa[],
		double	sm[],
		double	ss[],
		double	test,
		bool *const	usedZeroedSpecies
	)

Choose the optimum species basis for the calculations.

This is done by choosing the species with the largest mole fraction not currently a linear combination of the previous components. Then, calculate the stoichiometric coefficient matrix for that basis.

Rearranges the solution data to put the component data at the front of the species list.

Then, calculates m_stoichCoeffRxnMatrix(jcomp,irxn) the formation reactions for all noncomponent species in the mechanism. Also calculates DNG(I) and DNL(I), the net mole change for each formation reaction. Also, initializes IR(I) to the default state.

Parameters

[in]	doJustComponents	If true, the m_stoichCoeffRxnMatrix and m_deltaMolNumPhase are not calculated.
[in]	aw	Vector of mole fractions which will be used to construct an optimal basis from.
[in]	sa	Gram-Schmidt orthog work space (nc in length) sa[j]
[in]	ss	Gram-Schmidt orthog work space (nc in length) ss[j]
[in]	sm	QR matrix work space (ncne in length) sm[i+jne]
[in]	test	This is a small negative number dependent upon whether an estimate is supplied or not.
[out]	usedZeroedSpecies	If true, then a species with a zero concentration was used as a component. The problem may be converged. Or, the problem may have a range space error and may not have a proper solution.

Returns: VCS_SUCCESS if everything went ok. Returns VCS_FAILED_CONVERGENCE if there is a problem.

Internal Variables calculated by this routine:

m_numComponents: Number of component species. This routine calculates the m_numComponents species. It switches their positions in the species vector so that they occupy the first m_numComponents spots in the species vector.
m_stoichCoeffRxnMatrix(jcomp,irxn) Stoichiometric coefficient matrix for the reaction mechanism expressed in Reduced Canonical Form. jcomp refers to the component number, and irxn refers to the irxn_th non-component species.
m_deltaMolNumPhase(iphase,irxn): Change in the number of moles in phase, iphase, due to the noncomponent formation reaction, irxn.
m_phaseParticipation(iphase,irxn): This is 1 if the phase, iphase, participates in the formation reaction, irxn, and zero otherwise.

Definition at line 2015 of file vcs_solve_TP.cpp.

◆ vcs_basisOptMax()

size_t vcs_basisOptMax	(	const double *const	molNum,
		const size_t	j,
		const size_t	n
	)

Choose a species to test for the next component.

We make the choice based on testing (molNum[i] * spSize[i]) for its maximum value. Preference for single species phases is also made.

Parameters

molNum	Mole number vector
j	index into molNum[] that indicates where the search will start from Previous successful components are swapped into the front of molNum[].
n	Length of molNum[]

Definition at line 2499 of file vcs_solve_TP.cpp.

◆ vcs_species_type()

int vcs_species_type ( const size_t kspec ) const

Evaluate the species category for the indicated species.

All evaluations are done using the "old" version of the solution.

Parameters

kspec Species to be evaluated

Returns: the calculated species type

Definition at line 2550 of file vcs_solve_TP.cpp.

◆ vcs_evaluate_speciesType()

bool vcs_evaluate_speciesType ( )

This routine evaluates the species type for all species.

VCS_SPECIES_MAJOR: Major species
VCS_SPECIES_MINOR: Minor species
VCS_SPECIES_SMALLMS: The species lies in a multicomponent phase that exists. Its concentration is currently very low, necessitating a different method of calculation.
VCS_SPECIES_ZEROEDMS: The species lies in a multicomponent phase which currently doesn't exist. Its concentration is currently zero.
VCS_SPECIES_ZEROEDSS: Species lies in a single-species phase which is currently zeroed out.
VCS_SPECIES_DELETED: Species has such a small mole fraction it is deleted even though its phase may possibly exist. The species is believed to have such a small mole fraction that it best to throw the calculation of it out. It will be added back in at the end of the calculation.
VCS_SPECIES_INTERFACIALVOLTAGE: Species refers to an electron in the metal The unknown is equal to the interfacial voltage drop across the interface on the SHE (standard hydrogen electrode) scale (volts).
VCS_SPECIES_ZEROEDPHASE: Species lies in a multicomponent phase that is zeroed atm and will stay deleted due to a choice from a higher level. These species will formally always have zero mole numbers in the solution vector.
VCS_SPECIES_ACTIVEBUTZERO: The species lies in a multicomponent phase which currently does exist. Its concentration is currently identically zero, though the phase exists. Note, this is a temporary condition that exists at the start of an equilibrium problem. The species is soon "birthed" or "deleted".
VCS_SPECIES_STOICHZERO: The species lies in a multicomponent phase which currently does exist. Its concentration is currently identically zero, though the phase exists. This is a permanent condition due to stoich constraints

Definition at line 3007 of file vcs_solve_TP.cpp.

◆ vcs_dfe()

void vcs_dfe	(	const int	stateCalc,
		const int	ll,
		const size_t	lbot,
		const size_t	ltop
	)

Calculate the dimensionless chemical potentials of all species or of certain groups of species, at a fixed temperature and pressure.

We calculate the dimensionless chemical potentials of all species or certain groups of species here, at a fixed temperature and pressure, for the input mole vector z[] in the parameter list. Nondimensionalization is achieved by division by RT.

Note, for multispecies phases which are currently zeroed out, the chemical potential is filled out with the standard chemical potential.

For species in multispecies phases whose concentration is zero, we need to set the mole fraction to a very low value. Its chemical potential is then calculated using the VCS_DELETE_MINORSPECIES_CUTOFF concentration to keep numbers positive.

For formulas, see vcs_chemPotPhase().

Handling of Small Species:

As per the discussion above, for small species where the mole fraction

z(i) < VCS_DELETE_MINORSPECIES_CUTOFF

The chemical potential is calculated as:

 m_feSpecies(I)(I) = m_SSfeSpecies(I) + ln(ActCoeff[i](VCS_DELETE_MINORSPECIES_CUTOFF))

Species in the following categories are treated as "small species"

For species in multispecies phases which are currently not active, the treatment is different. These species are in the following species categories:

For these species, the ln( ActCoeff[I] X[I]) term is dropped altogether. The following equation is used:

m_feSpecies(I) = m_SSfeSpecies(I)
               + Charge[I] * Faraday_dim * phasePhi[iphase];

Handling of "Species" Representing Interfacial Voltages

These species have species types of VCS_SPECIES_TYPE_INTERFACIALVOLTAGE The chemical potentials for these "species" refer to electrons in metal electrodes. They have the following formula

m_feSpecies(I) = m_SSfeSpecies(I) - F z[I] / RT

F is Faraday's constant.
R = gas constant
T = temperature
V = potential of the interface = phi_electrode - phi_solution

For these species, the solution vector unknown, z[I], is V, the phase voltage, in volts.

Parameters

ll	Determine which group of species gets updated `ll = 0`: Calculate for all species `ll < 0`: calculate for components and for major non-components `ll = 1`: calculate for components and for minor non-components
lbot	Restricts the calculation of the chemical potential to the species between LBOT <= i < LTOP. Usually LBOT and LTOP will be equal to 0 and MR, respectively.
ltop	Top value of the loops
stateCalc	Determines whether z is old or new or tentative: 1: Use the tentative values for the total number of moles in the phases, that is, use TG1 instead of TG etc. 0: Use the base values of the total number of moles in each system.

Also needed: ff : standard state chemical potentials. These are the chemical potentials of the standard states at the same T and P as the solution. tg : Total Number of moles in the phase.

Definition at line 2703 of file vcs_solve_TP.cpp.

◆ vcs_updateVP()

void vcs_updateVP ( const int stateCalc )

This routine uploads the state of the system into all of the vcs_VolumePhase objects in the current problem.

Parameters

stateCalc

Determines where to get the mole numbers from.

VCS_STATECALC_OLD -> from m_molNumSpecies_old
VCS_STATECALC_NEW -> from m_molNumSpecies_new

Definition at line 2988 of file vcs_solve_TP.cpp.

◆ vcs_popPhasePossible()

bool vcs_popPhasePossible ( const size_t iphasePop ) const

Utility function that evaluates whether a phase can be popped into existence.

A phase can be popped iff the stoichiometric coefficients for the component species, whose concentrations will be lowered during the process, are positive by at least a small degree.

If one of the phase species is a zeroed component, then the phase can be popped if the component increases in mole number as the phase moles are increased.

Parameters

iphasePop id of the phase, which is currently zeroed,

Returns: true if the phase can come into existence and false otherwise.

Definition at line 528 of file vcs_solve.cpp.

◆ vcs_popPhaseID()

size_t vcs_popPhaseID ( vector< size_t > & phasePopPhaseIDs )

Decision as to whether a phase pops back into existence.

Parameters

phasePopPhaseIDs Vector containing the phase ids of the phases that will be popped this step.

Returns: the phase id of the phase that pops back into existence. Returns -1 if there are no phases

Definition at line 617 of file vcs_solve.cpp.

◆ vcs_popPhaseRxnStepSizes()

int vcs_popPhaseRxnStepSizes ( const size_t iphasePop )

Calculates the deltas of the reactions due to phases popping into existence.

Updates m_deltaMolNumSpecies[irxn] : reaction adjustments, where irxn refers to the irxn'th species formation reaction. This adjustment is for species irxn + M, where M is the number of components.

Parameters

iphasePop Phase id of the phase that will come into existence

Returns

an int representing the status of the step

0 : normal return
1 : A single species phase species has been zeroed out in this routine. The species is a noncomponent
2 : Same as one but, the zeroed species is a component.
3 : Nothing was done because the phase couldn't be birthed because a needed component is zero.

Definition at line 708 of file vcs_solve.cpp.

◆ vcs_RxnStepSizes()

size_t vcs_RxnStepSizes	(	int &	forceComponentCalc,
		size_t &	kSpecial
	)

Calculates formation reaction step sizes.

This is equation 6.4-16, p. 143 in Smith and Missen [40].

Output

m_deltaMolNumSpecies(irxn) : reaction adjustments, where irxn refers to the irxn'th species formation reaction. This adjustment is for species irxn + M, where M is the number of components.

Special branching occurs sometimes. This causes the component basis to be reevaluated

Parameters

forceComponentCalc	integer flagging whether a component recalculation needs to be carried out.
kSpecial	species number of phase being zeroed.

Returns: an int representing which phase may need to be zeroed

Definition at line 857 of file vcs_solve.cpp.

◆ vcs_tmoles()

double vcs_tmoles ( )

Calculates the total number of moles of species in all phases.

Also updates the variable m_totalMolNum and Reconciles Phase existence flags with total moles in each phase.

Definition at line 2945 of file vcs_solve_TP.cpp.

◆ vcs_deltag()

void vcs_deltag	(	const int	L,
		const bool	doDeleted,
		const int	vcsState,
		const bool	alterZeroedPhases = `true`
	)

This subroutine calculates reaction free energy changes for all noncomponent formation reactions.

Formation reactions are reactions which create each noncomponent species from the component species. m_stoichCoeffRxnMatrix(jcomp,irxn) are the stoichiometric coefficients for these reactions. A stoichiometric coefficient of one is assumed for species irxn in this reaction.

Parameters

L	`L < 0`: Calculate reactions corresponding to major noncomponent and zeroed species only `L = 0`: Do all noncomponent reactions, i, between 0 <= i < irxnl `L > 0`: Calculate reactions corresponding to minor noncomponent and zeroed species only
doDeleted	Do deleted species
vcsState	Calculate deltaG corresponding to either old or new free energies
alterZeroedPhases	boolean indicating whether we should add in a special section for zeroed phases.

Note we special case one important issue. If the component has zero moles, then we do not allow deltaG < 0.0 for formation reactions which would lead to the loss of more of that same component. This dG < 0.0 condition feeds back into the algorithm in several places, and leads to a infinite loop in at least one case.

Definition at line 3073 of file vcs_solve_TP.cpp.

◆ vcs_switch_pos()

void vcs_switch_pos	(	const bool	ifunc,
		const size_t	k1,
		const size_t	k2
	)

Swaps the indices for all of the global data for two species, k1 and k2.

Parameters

ifunc	If true, switch the species data and the noncomponent reaction data. This must be called for a non-component species only. If false, switch the species data only. Typically, we use this option when determining the component species and at the end of the calculation, when we want to return unscrambled results. All rxn data will be out-of-date.
k1	First species index
k2	Second species index

Definition at line 3381 of file vcs_solve_TP.cpp.

◆ vcs_phaseStabilityTest()

double vcs_phaseStabilityTest ( const size_t iph )

Main program to test whether a deleted phase should be brought back into existence.

Parameters

iph	Phase id of the deleted phase

Definition at line 1136 of file vcs_solve.cpp.

◆ vcs_TP()

int vcs_TP	(	int	ipr,
		int	ip1,
		int	maxit,
		double	T,
		double	pres
	)

Solve an equilibrium problem at a particular fixed temperature and pressure.

The actual problem statement is assumed to be in the structure already. This is a wrapper around the solve_TP() function. In this wrapper, we calculate the standard state Gibbs free energies of the species and we decide whether to we need to use the initial guess algorithm.

Parameters

ipr	= 1 -> Print results to standard output; 0 -> don't report on anything
ip1	= 1 -> Print intermediate results; 0 -> Dont print any intermediate results
maxit	Maximum number of iterations for the algorithm
T	Value of the Temperature (Kelvin)
pres	Value of the Pressure

Returns

an integer representing the success of the algorithm

0 = Equilibrium Achieved
1 = Range space error encountered. The element abundance criteria are only partially satisfied. Specifically, the first NC= (number of components) conditions are satisfied. However, the full NE (number of elements) conditions are not satisfied. The equilibrium condition is returned.
-1 = Maximum number of iterations is exceeded. Convergence was not found.

Definition at line 1399 of file vcs_solve.cpp.

◆ vcs_evalSS_TP()

int vcs_evalSS_TP	(	int	ipr,
		int	ip1,
		double	Temp,
		double	pres
	)

Evaluate the standard state free energies at the current temperature and pressure.

Ideal gas pressure contribution is added in here.

Parameters

ipr	1 -> Print results to standard output; 0 -> don't report on anything
ip1	1 -> Print intermediate results; 0 -> don't.
Temp	Temperature (Kelvin)
pres	Pressure (Pascal)

Definition at line 1431 of file vcs_solve.cpp.

◆ vcs_fePrep_TP()

void vcs_fePrep_TP ( )

Initialize the chemical potential of single species phases.

For single species phases, initialize the chemical potential with the value of the standard state chemical potential. This value doesn't change during the calculation

Definition at line 1445 of file vcs_solve.cpp.

◆ vcs_VolTotal()

double vcs_VolTotal	(	const double	tkelvin,
		const double	pres,
		const double	w[],
		double	volPM[]
	)

Calculation of the total volume and the partial molar volumes.

This function calculates the partial molar volume for all species, kspec, in the thermo problem at the temperature TKelvin and pressure, Pres, pres is in atm. And, it calculates the total volume of the combined system.

Parameters

[in]	tkelvin	Temperature in kelvin()
[in]	pres	Pressure in Pascal
[in]	w	w[] is the vector containing the current mole numbers in units of kmol.
[out]	volPM[]	For species in all phase, the entries are the partial molar volumes units of M**3 / kmol.

Returns: the total volume of the entire system in units of m**3.

Definition at line 1458 of file vcs_solve.cpp.

◆ vcs_prep()

int vcs_prep ( int printLvl )

This routine is mostly concerned with changing the private data to be consistent with what's needed for solution.

It is called one time for each new problem structure definition.

The problem structure refers to:

the number and identity of the species.
the formula matrix and thus the number of components.
the number and identity of the phases.
the equation of state
the method and parameters for determining the standard state
The method and parameters for determining the activity coefficients.

Tasks:

Fill in the SSPhase[] array.
Check to see if any multispecies phases actually have only one species in that phase. If true, reassign that phase and species to be a single-species phase.
Determine the number of components in the problem if not already done so. During this process the order of the species is changed in the private data structure. All references to the species properties must employ the ind[] index vector.
Initialization of arrays to zero.
Check to see if the problem is well posed (If all the element abundances are zero, the algorithm will fail)

Parameters

printLvl Print level of the routine

Returns: VCS_SUCCESS = everything went OK; VCS_PUB_BAD = There is an irreconcilable difference in the public data structure from when the problem was initially set up.

Definition at line 1472 of file vcs_solve.cpp.

◆ vcs_elem_rearrange()

int vcs_elem_rearrange	(	double *const	aw,
		double *const	sa,
		double *const	sm,
		double *const	ss
	)

Rearrange the constraint equations represented by the Formula Matrix so that the operational ones are in the front.

This subroutine handles the rearrangement of the constraint equations represented by the Formula Matrix. Rearrangement is only necessary when the number of components is less than the number of elements. For this case, some constraints can never be satisfied exactly, because the range space represented by the Formula Matrix of the components can't span the extra space. These constraints, which are out of the range space of the component Formula matrix entries, are migrated to the back of the Formula matrix.

A prototypical example is an extra element column in FormulaMatrix[], which is identically zero. For example, let's say that argon is has an element column in FormulaMatrix[], but no species in the mechanism actually contains argon. Then, nc < ne. Also, without perturbation of FormulaMatrix[] vcs_basopt[] would produce a zero pivot because the matrix would be singular (unless the argon element column was already the last column of FormulaMatrix[].

This routine borrows heavily from vcs_basopt's algorithm. It finds nc constraints which span the range space of the Component Formula matrix, and assigns them as the first nc components in the formula matrix. This guarantees that vcs_basopt[] has a nonsingular matrix to invert.

Other Variables

Parameters

aw	Mole fraction work space (ne in length)
sa	Gram-Schmidt orthog work space (ne in length)
sm	QR matrix work space (ne*ne in length)
ss	Gram-Schmidt orthog work space (ne in length)

Definition at line 1627 of file vcs_solve.cpp.

◆ vcs_switch_elem_pos()

void vcs_switch_elem_pos	(	size_t	ipos,
		size_t	jpos
	)

Swaps the indices for all of the global data for two elements, ipos and jpos.

This function knows all of the element information with VCS_SOLVE, and can therefore switch element positions

Parameters

ipos	first global element index
jpos	second global element index

Definition at line 1743 of file vcs_solve.cpp.

◆ vcs_Hessian_diag_adj()

double vcs_Hessian_diag_adj	(	size_t	irxn,
		double	hessianDiag_Ideal
	)

Calculates the diagonal contribution to the Hessian due to the dependence of the activity coefficients on the mole numbers.

(See framemaker notes, Eqn. 20 - VCS Equations document)

We allow the diagonal to be increased positively to any degree. We allow the diagonal to be decreased to 1/3 of the ideal solution value, but no more -> it must remain positive.

Definition at line 1776 of file vcs_solve.cpp.

◆ vcs_Hessian_actCoeff_diag()

double vcs_Hessian_actCoeff_diag ( size_t irxn )

Calculates the diagonal contribution to the Hessian due to the dependence of the activity coefficients on the mole numbers.

(See framemaker notes, Eqn. 20 - VCS Equations document)

Definition at line 1794 of file vcs_solve.cpp.

◆ vcs_CalcLnActCoeffJac()

void vcs_CalcLnActCoeffJac ( const double *const moleSpeciesVCS )

Recalculate all of the activity coefficients in all of the phases based on input mole numbers.

Parameters

moleSpeciesVCS kmol of species to be used in the update.

NOTE: This routine needs to be regulated.

Definition at line 1824 of file vcs_solve.cpp.

◆ vcs_report()

int vcs_report ( int iconv )

Print out a report on the state of the equilibrium problem to standard output.

Parameters

iconv

Indicator of convergence, to be printed out in the report:

0 converged
1 range space error
-1 not converged

Definition at line 1842 of file vcs_solve.cpp.

◆ vcs_elab()

void vcs_elab ( )

Computes the current elemental abundances vector.

Computes the elemental abundances vector, m_elemAbundances[], and stores it back into the global structure

Definition at line 2128 of file vcs_solve.cpp.

◆ vcs_elabcheck()

bool vcs_elabcheck ( int ibound )

Checks to see if the element abundances are in compliance.

If they are, then TRUE is returned. If not, FALSE is returned. Note the number of constraints checked is usually equal to the number of components in the problem. This routine can check satisfaction of all of the constraints in the problem, which is equal to ne. However, the solver can't fix breakage of constraints above nc, because that nc is the range space by definition. Satisfaction of extra constraints would have had to occur in the problem specification.

The constraints should be broken up into 2 sections. If a constraint involves a formula matrix with positive and negative signs, and eaSet = 0.0, then you can't expect that the sum will be zero. There may be roundoff that inhibits this. However, if the formula matrix is all of one sign, then this requires that all species with nonzero entries in the formula matrix be identically zero. We put this into the logic below.

Parameters

ibound 1: Checks constraints up to the number of elements; 0: Checks constraints up to the number of components.

Definition at line 2140 of file vcs_solve.cpp.

◆ vcs_elabPhase()

void vcs_elabPhase	(	size_t	iphase,
		double *const	elemAbundPhase
	)

Computes the elemental abundances vector for a single phase, elemAbundPhase[], and returns it through the argument list.

The mole numbers of species are taken from the current value in m_molNumSpecies_old[].

Definition at line 2196 of file vcs_solve.cpp.

◆ vcs_elcorr()

int vcs_elcorr	(	double	aa[],
		double	x[]
	)

This subroutine corrects for element abundances.

At the end of the subroutine, the total moles in all phases are recalculated again, because we have changed the number of moles in this routine.

Parameters

aa	temporary work vector, length ne*ne
x	temporary work vector, length ne

Returns

0 = Nothing of significance happened, Element abundances were and still are good.
1 = The solution changed significantly; The element abundances are now good.
2 = The solution changed significantly, The element abundances are still bad.
3 = The solution changed significantly, The element abundances are still bad and a component species got zeroed out.

Internal data to be worked on::
- ga Current element abundances
- m_elemAbundancesGoal Required elemental abundances
- m_molNumSpecies_old Current mole number of species.
- m_formulaMatrix[][] Formula matrix of the species
- ne Number of elements
- nc Number of components.

NOTES: This routine is turning out to be very problematic. There are lots of special cases and problems with zeroing out species.

Still need to check out when we do loops over nc vs. ne.

Definition at line 2208 of file vcs_solve.cpp.

◆ vcs_inest_TP()

int vcs_inest_TP ( )

Create an initial estimate of the solution to the thermodynamic equilibrium problem.

Returns

value indicates success:

0: successful initial guess
-1: Unsuccessful initial guess; the elemental abundances aren't satisfied.

Definition at line 2550 of file vcs_solve.cpp.

◆ vcs_setMolesLinProg()

int vcs_setMolesLinProg ( )

Estimate the initial mole numbers by constrained linear programming.

This is done by running each reaction as far forward or backward as possible, subject to the constraint that all mole numbers remain non- negative. Reactions for which \( \Delta \mu^0 \) are positive are run in reverse, and ones for which it is negative are run in the forward direction. The end result is equivalent to solving the linear programming problem of minimizing the linear Gibbs function subject to the element and non-negativity constraints.

Definition at line 2647 of file vcs_solve.cpp.

◆ vcs_Total_Gibbs()

double vcs_Total_Gibbs	(	double *	w,
		double *	fe,
		double *	tPhMoles
	)

Calculate the total dimensionless Gibbs free energy.

Inert species are handled as if they had a standard free energy of zero. Note, for this algorithm this function should be monotonically decreasing.

Definition at line 2784 of file vcs_solve.cpp.

◆ vcs_GibbsPhase()

double vcs_GibbsPhase	(	size_t	iphase,
		const double *const	w,
		const double *const	fe
	)

Calculate the total dimensionless Gibbs free energy of a single phase.

Inert species are handled as if they had a standard free energy of zero and if they obeyed ideal solution/gas theory.

Parameters

iphase	ID of the phase
w	Species mole number vector for all species
fe	vector of partial molar free energies of all of the species

Definition at line 2809 of file vcs_solve.cpp.

◆ vcs_prob_update()

void vcs_prob_update ( )

Transfer the results of the equilibrium calculation back from VCS_SOLVE.

Definition at line 2833 of file vcs_solve.cpp.

◆ vcs_prob_specifyFully()

void vcs_prob_specifyFully ( )

Fully specify the problem to be solved.

Definition at line 2846 of file vcs_solve.cpp.

◆ vcs_zero_species()

int vcs_zero_species ( const size_t kspec )

private

Zero out the concentration of a species.

Make sure to conserve elements and keep track of the total moles in all phases.

w[]
m_tPhaseMoles_old[]

Parameters

kspec Species index

Returns: : 1: succeeded 0: failed.

Definition at line 1492 of file vcs_solve_TP.cpp.

◆ vcs_delete_species()

int vcs_delete_species ( const size_t kspec )

private

Change a single species from active to inactive status.

Rearrange data when species is added or removed. The Lth species is moved to the back of the species vector. The back of the species vector is indicated by the value of MR, the current number of active species in the mechanism.

Parameters

kspec Species Index

Returns: Returns 0 unless. The return is 1 when the current number of noncomponent species is equal to zero. A recheck of deleted species is carried out in the main code.

Definition at line 1511 of file vcs_solve_TP.cpp.

◆ vcs_delete_multiphase()

bool vcs_delete_multiphase ( const size_t iph )

private

This routine handles the bookkeeping involved with the deletion of multiphase phases from the problem.

When they are deleted, all of their species become active species, even though their mole numbers are set to zero. The routine does not make the decision to eliminate multiphases.

Note, species in phases with zero mole numbers are still considered active. Whether the phase pops back into existence or not is checked as part of the main iteration loop.

Parameters

iph	Phase to be deleted

Returns: whether the operation was successful or not

Definition at line 1623 of file vcs_solve_TP.cpp.

◆ delta_species()

int delta_species	(	const size_t	kspec,
		double *const	delta_ptr
	)

private

Change the concentration of a species by delta moles.

Make sure to conserve elements and keep track of the total kmoles in all phases.

Parameters

kspec	The species index
delta_ptr	pointer to the delta for the species. This may change during the calculation

Returns: 1: succeeded without change of dx 0: Had to adjust dx, perhaps to zero, in order to do the delta.

Definition at line 1443 of file vcs_solve_TP.cpp.

◆ vcs_add_all_deleted()

size_t vcs_add_all_deleted ( )

private

Provide an estimate for the deleted species in phases that are not zeroed out.

Try to add back in all deleted species. An estimate of the kmol numbers are obtained and the species is added back into the equation system, into the old state vector.

This routine is called at the end of the calculation, just before returning to the user.

Definition at line 1831 of file vcs_solve_TP.cpp.

◆ vcs_recheck_deleted()

int vcs_recheck_deleted ( )

private

Recheck deleted species in multispecies phases.

We are checking the equation:

    sum_u = sum_j_comp [ sigma_i_j * u_j ]
          = u_i_O + \ln((AC_i * W_i)/m_tPhaseMoles_old)

by first evaluating:

     DG_i_O = u_i_O - sum_u.

Then, if TL is zero, the phase pops into existence if DG_i_O < 0. Also, if the phase exists, then we check to see if the species can have a mole number larger than VCS_DELETE_SPECIES_CUTOFF (default value = 1.0E-32).

Definition at line 1757 of file vcs_solve_TP.cpp.

◆ vcs_minor_alt_calc()

double vcs_minor_alt_calc	(	size_t	kspec,
		size_t	irxn,
		bool *	do_delete,
		char *	ANOTE = `0`
	)		const

private

Minor species alternative calculation.

This is based upon the following approximation: The mole fraction changes due to these reactions don't affect the mole numbers of the component species. Therefore the following approximation is valid for a small component of an ideal phase:

  0 = m_deltaGRxn_old(I) + log(molNum_new(I)/molNum_old(I))

m_deltaGRxn_old contains the contribution from

  m_feSpecies_old(I) =
         m_SSfeSpecies(I) +
         log(ActCoeff[i] * molNum_old(I) / m_tPhaseMoles_old(iph))

Thus,

  molNum_new(I)= molNum_old(I) * EXP(-m_deltaGRxn_old(I))

Most of this section is mainly restricting the update to reasonable values. We restrict the update a factor of 1.0E10 up and 1.0E-10 down because we run into trouble with the addition operator due to roundoff if we go larger than ~1.0E15. Roundoff will then sometimes produce zero mole fractions.

Note: This routine was generalized to incorporate nonideal phases and phases on the molality basis

Parameters

[in]	kspec	The current species and corresponding formation reaction number.
[in]	irxn	The current species and corresponding formation reaction number.
[out]	do_delete	BOOLEAN which if true on return, then we branch to the section that deletes a species from the current set of active species.
[out]	ANOTE	Buffer used for debug annotations

Definition at line 1360 of file vcs_solve_TP.cpp.

◆ vcs_globStepDamp()

bool vcs_globStepDamp ( )

private

This routine optimizes the minimization of the total Gibbs free energy by making sure the slope of the following functional stays negative:

The slope of the following functional is equivalent to the slope of the total Gibbs free energy of the system:

 d_Gibbs/ds = sum_k( m_deltaGRxn * m_deltaMolNumSpecies[k] )

along the current direction m_deltaMolNumSpecies[], by choosing a value, al: (0<al<1) such that the a parabola approximation to Gibbs(al) fit to the end points al = 0 and al = 1 is minimized.

s1 = slope of Gibbs function at al = 0, which is the previous solution = d(Gibbs)/d(al).
s2 = slope of Gibbs function at al = 1, which is the current solution = d(Gibbs)/d(al).

Only if there has been an inflection point (that is, s1 < 0 and s2 > 0), does this code section kick in. It finds the point on the parabola where the slope is equal to zero.

Definition at line 1924 of file vcs_solve_TP.cpp.

◆ l2normdg()

double l2normdg ( double dg[] ) const

private

Calculate the norm of a deltaGibbs free energy vector.

Positive DG for species which don't exist are ignored.

Parameters

dg	Vector of local delta G's.

Definition at line 2927 of file vcs_solve_TP.cpp.

◆ vcs_inest()

void vcs_inest	(	double *const	aw,
		double *const	sa,
		double *const	sm,
		double *const	ss,
		double	test
	)

private

Estimate equilibrium compositions.

Algorithm covered in a section of Smith and Missen's Book [40].

Linear programming module is based on using dbolm.

Parameters

aw	aw[i[ Mole fraction work space (ne in length)
sa	sa[j] = Gram-Schmidt orthog work space (ne in length)
sm	sm[i+jne] = QR matrix work space (nene in length)
ss	ss[j] = Gram-Schmidt orthog work space (ne in length)
test	This is a small negative number.

Definition at line 2935 of file vcs_solve.cpp.

◆ vcs_SSPhase()

void vcs_SSPhase ( )

private

Calculate the status of single species phases.

Definition at line 3195 of file vcs_solve.cpp.

◆ vcs_delete_memory()

void vcs_delete_memory ( )

private

Delete memory that isn't just resizable STL containers.

This gets called by the destructor or by InitSizes().

Definition at line 3230 of file vcs_solve.cpp.

◆ vcs_counters_init()

void vcs_counters_init ( int ifunc )

private

Initialize the internal counters.

Initialize the internal counters containing the subroutine call values and times spent in the subroutines.

ifunc = 0 Initialize only those counters appropriate for the top of vcs_solve_TP(). = 1 Initialize all counters.

Definition at line 3241 of file vcs_solve.cpp.

◆ vcs_TCounters_report()

void vcs_TCounters_report ( int timing_print_lvl = 1 )

private

Create a report on the plog file containing timing and its information.

Parameters

timing_print_lvl If 0, just report the iteration count. If larger than zero, report the timing information

Definition at line 3259 of file vcs_solve.cpp.

◆ vcs_updateMolNumVolPhases()

void vcs_updateMolNumVolPhases ( const int stateCalc )

private

Update all underlying vcs_VolPhase objects.

Update the mole numbers and the phase voltages of all phases in the vcs problem

Parameters

stateCalc Location of the update (either VCS_STATECALC_NEW or VCS_STATECALC_OLD).

Definition at line 3484 of file vcs_solve_TP.cpp.

◆ prob_report()

void prob_report ( int print_lvl )

Print out the problem specification in all generality as it currently exists in the VCS_SOLVE object.

Parameters

print_lvl

Parameter lvl for printing

0 - no printing
1 - all printing

Definition at line 3285 of file vcs_solve.cpp.

◆ addPhaseElements()

void addPhaseElements ( vcs_VolPhase * volPhase )

Add elements to the local element list.

This routine sorts through the elements defined in the vcs_VolPhase object. It then adds the new elements to the VCS_SOLVE object, and creates a global map, which is stored in the vcs_VolPhase object. Id and matching of elements is done strictly via the element name, with case not mattering.

The routine also fills in the position of the element in the vcs_VolPhase object's ElGlobalIndex field.

Parameters

volPhase Object containing the phase to be added. The elements in this phase are parsed for addition to the global element list

Definition at line 3382 of file vcs_solve.cpp.

◆ addOnePhaseSpecies()

size_t addOnePhaseSpecies	(	vcs_VolPhase *	volPhase,
		size_t	k,
		size_t	kT
	)

This routines adds entries for the formula matrix for one species.

This routines adds entries for the formula matrix for this object for one species

This object also fills in the index filed, IndSpecies, within the volPhase object.

Parameters

volPhase	object containing the species
k	Species number within the volPhase k
kT	global Species number within this object

Definition at line 3408 of file vcs_solve.cpp.

◆ addElement()

size_t addElement	(	const char *	elNameNew,
		int	elType,
		int	elactive
	)

This routine resizes the number of elements in the VCS_SOLVE object by adding a new element to the end of the element list.

The element name is added. Formula vector entries ang element abundances for the new element are set to zero.

Parameters

elNameNew	New name of the element
elType	Type of the element
elactive	boolean indicating whether the element is active

Returns: the index number of the new element

Definition at line 3428 of file vcs_solve.cpp.

◆ disableTiming()

void disableTiming ( )

static

Disable printing of timing information.

Used to generate consistent output for tests.

Definition at line 3448 of file vcs_solve.cpp.

Member Data Documentation

◆ m_printLvl

int m_printLvl

Print level for print routines.

Definition at line 985 of file vcs_solve.h.

◆ m_nsp

size_t m_nsp

Total number of species in the problems.

Definition at line 1045 of file vcs_solve.h.

◆ m_nelem

size_t m_nelem = 0

Number of element constraints in the problem.

Definition at line 1048 of file vcs_solve.h.

◆ m_numComponents

size_t m_numComponents = 0

Number of components calculated for the problem.

Definition at line 1051 of file vcs_solve.h.

◆ m_numRxnTot

size_t m_numRxnTot = 0

Total number of non-component species in the problem.

Definition at line 1054 of file vcs_solve.h.

◆ m_numSpeciesRdc

size_t m_numSpeciesRdc

Current number of species in the problems.

Species can be deleted if they aren't stable under the current conditions

Definition at line 1058 of file vcs_solve.h.

◆ m_numRxnRdc

size_t m_numRxnRdc = 0

Current number of non-component species in the problem.

Species can be deleted if they aren't stable under the current conditions

Definition at line 1062 of file vcs_solve.h.

◆ m_numRxnMinorZeroed

size_t m_numRxnMinorZeroed = 0

Number of active species which are currently either treated as minor species.

Definition at line 1066 of file vcs_solve.h.

◆ m_numPhases

size_t m_numPhases

Number of Phases in the problem.

Definition at line 1069 of file vcs_solve.h.

◆ m_formulaMatrix

Array2D m_formulaMatrix

Formula matrix for the problem.

FormulaMatrix(kspec,j) = Number of elements, j, in the kspec species

Both element and species indices are swapped.

Definition at line 1077 of file vcs_solve.h.

◆ m_stoichCoeffRxnMatrix

Array2D m_stoichCoeffRxnMatrix

Stoichiometric coefficient matrix for the reaction mechanism expressed in Reduced Canonical Form.

This is the stoichiometric coefficient matrix for the reaction which forms species kspec from the component species. A stoichiometric coefficient of one is assumed for the species kspec in this mechanism.

NOTE: kspec = irxn + m_numComponents

m_stoichCoeffRxnMatrix(j,irxn) : j refers to the component number, and irxn refers to the irxn_th non-component species. The stoichiometric coefficients multiplied by the Formula coefficients of the component species add up to the negative value of the number of elements in the species kspec.

size = nelements0 x nspecies0

Definition at line 1096 of file vcs_solve.h.

◆ m_scSize

vector<double> m_scSize

Absolute size of the stoichiometric coefficients.

scSize[irxn] = abs(Size) of the stoichiometric coefficients. These are used to determine whether a given species should be handled by the alt_min treatment or should be handled as a major species.

Definition at line 1105 of file vcs_solve.h.

◆ m_spSize

vector<double> m_spSize

total size of the species

This is used as a multiplier to the mole number in figuring out which species should be components.

Definition at line 1112 of file vcs_solve.h.

◆ m_SSfeSpecies

vector<double> m_SSfeSpecies

Standard state chemical potentials for species K at the current temperature and pressure.

The first NC entries are for components. The following NR entries are for the current non-component species in the mechanism.

Definition at line 1120 of file vcs_solve.h.

◆ m_feSpecies_old

vector<double> m_feSpecies_old

Free energy vector from the start of the current iteration.

The free energies are saved at the start of the current iteration. Length = number of species

Definition at line 1127 of file vcs_solve.h.

◆ m_feSpecies_new

vector<double> m_feSpecies_new

Dimensionless new free energy for all the species in the mechanism at the new tentative T, P, and mole numbers.

The first NC entries are for components. The following NR entries are for the current non-component species in the mechanism. Length = number of species

Definition at line 1136 of file vcs_solve.h.

◆ m_doEstimateEquil

int m_doEstimateEquil = -1

Setting for whether to do an initial estimate.

Initial estimate: 0 Do not estimate the solution at all. Use the supplied mole numbers as is. 1 Only do an estimate if the element abundances aren't satisfied. -1 Force an estimate of the soln. Throw out the input mole numbers.

Definition at line 1146 of file vcs_solve.h.

◆ m_molNumSpecies_old

vector<double> m_molNumSpecies_old

Total moles of the species.

Total number of moles of the kth species. Length = Total number of species = m

Definition at line 1153 of file vcs_solve.h.

◆ m_speciesUnknownType

vector<int> m_speciesUnknownType

Specifies the species unknown type.

There are two types. One is the straightforward species, with the mole number w[k], as the unknown. The second is the an interfacial voltage where w[k] refers to the interfacial voltage in volts.

These species types correspond to metallic electrons corresponding to electrodes. The voltage and other interfacial conditions sets up an interfacial current, which is set to zero in this initial treatment. Later we may have non-zero interfacial currents.

Definition at line 1166 of file vcs_solve.h.

◆ m_deltaMolNumPhase

Array2D m_deltaMolNumPhase

Change in the number of moles of phase, iphase, due to the noncomponent formation reaction, irxn, for species, k:

m_deltaMolNumPhase(iphase,irxn) = k = nc + irxn

Definition at line 1173 of file vcs_solve.h.

◆ m_phaseParticipation

Array2D m_phaseParticipation

This is 1 if the phase, iphase, participates in the formation reaction irxn, and zero otherwise.

PhaseParticipation(iphase,irxn)

Definition at line 1177 of file vcs_solve.h.

◆ m_phasePhi

vector<double> m_phasePhi

electric potential of the iph phase

Definition at line 1180 of file vcs_solve.h.

◆ m_molNumSpecies_new

vector<double> m_molNumSpecies_new

Tentative value of the mole number vector.

It's also used to store the mole fraction vector.

Definition at line 1184 of file vcs_solve.h.

◆ m_deltaGRxn_new

vector<double> m_deltaGRxn_new

Delta G(irxn) for the noncomponent species in the mechanism.

Computed by the subroutine deltaG. m_deltaGRxn is the free energy change for the reaction which forms species K from the component species. This vector has length equal to the number of noncomponent species in the mechanism. It starts with the first current noncomponent species in the mechanism.

Definition at line 1194 of file vcs_solve.h.

◆ m_deltaGRxn_old

vector<double> m_deltaGRxn_old

Last deltag[irxn] from the previous step.

Definition at line 1197 of file vcs_solve.h.

◆ m_deltaGRxn_Deficient

vector<double> m_deltaGRxn_Deficient

Last deltag[irxn] from the previous step with additions for possible births of zeroed phases.

Definition at line 1201 of file vcs_solve.h.

◆ m_deltaGRxn_tmp

vector<double> m_deltaGRxn_tmp

Temporary vector of Rxn DeltaG's.

This is used from time to time, for printing purposes

Definition at line 1207 of file vcs_solve.h.

◆ m_deltaMolNumSpecies

vector<double> m_deltaMolNumSpecies

Reaction Adjustments for each species during the current step.

delta Moles for each species during the current step. Length = number of species

Definition at line 1214 of file vcs_solve.h.

◆ m_elemAbundances

vector<double> m_elemAbundances

Element abundances vector.

Vector of moles of each element actually in the solution vector. Except for certain parts of the algorithm, this is a constant. Note other constraint conditions are added to this vector. This is input from the input file and is considered a constant from thereon. units = kmoles

Definition at line 1223 of file vcs_solve.h.

◆ m_elemAbundancesGoal

vector<double> m_elemAbundancesGoal

Element abundances vector Goals.

Vector of moles of each element that are the goals of the simulation. This is a constant in the problem. Note other constraint conditions are added to this vector. This is input from the input file and is considered a constant from thereon. units = kmoles

Definition at line 1232 of file vcs_solve.h.

◆ m_totalMolNum

double m_totalMolNum = 0.0

Total number of kmoles in all phases.

This number includes the inerts. -> Don't use this except for scaling purposes

Definition at line 1239 of file vcs_solve.h.

◆ m_tPhaseMoles_old

vector<double> m_tPhaseMoles_old

Total kmols of species in each phase.

This contains the total number of moles of species in each phase

Length = number of phases

Definition at line 1247 of file vcs_solve.h.

◆ m_tPhaseMoles_new

vector<double> m_tPhaseMoles_new

total kmols of species in each phase in the tentative soln vector

This contains the total number of moles of species in each phase in the tentative solution vector

Length = number of phases

Definition at line 1256 of file vcs_solve.h.

◆ m_TmpPhase

vector<double> m_TmpPhase

mutable

Temporary vector of length NPhase.

Definition at line 1259 of file vcs_solve.h.

◆ m_TmpPhase2

vector<double> m_TmpPhase2

mutable

Temporary vector of length NPhase.

Definition at line 1262 of file vcs_solve.h.

◆ m_deltaPhaseMoles

vector<double> m_deltaPhaseMoles

Change in the total moles in each phase.

Length number of phases.

Definition at line 1268 of file vcs_solve.h.

◆ m_temperature

double m_temperature

Temperature (Kelvin)

Definition at line 1271 of file vcs_solve.h.

◆ m_pressurePA

double m_pressurePA

Pressure.

Definition at line 1274 of file vcs_solve.h.

◆ TPhInertMoles

vector<double> TPhInertMoles

Total kmoles of inert to add to each phase.

TPhInertMoles[iph] = Total kmoles of inert to add to each phase length = number of phases

Definition at line 1281 of file vcs_solve.h.

◆ m_tolmaj

double m_tolmaj = 1e-8

Tolerance requirement for major species.

Definition at line 1284 of file vcs_solve.h.

◆ m_tolmin

double m_tolmin = 1e-6

Tolerance requirements for minor species.

Definition at line 1287 of file vcs_solve.h.

◆ m_tolmaj2

double m_tolmaj2 = 1e-10

Below this, major species aren't refined any more.

Definition at line 1290 of file vcs_solve.h.

◆ m_tolmin2

double m_tolmin2 = 1e-8

Below this, minor species aren't refined any more.

Definition at line 1293 of file vcs_solve.h.

◆ m_speciesMapIndex

vector<size_t> m_speciesMapIndex

Index vector that keeps track of the species vector rearrangement.

At the end of each run, the species vector and associated data gets put back in the original order.

Example

k = m_speciesMapIndex[kspec]

kspec = current order in the vcs_solve object
k     = original order in the MultiPhase object

Definition at line 1307 of file vcs_solve.h.

◆ m_speciesLocalPhaseIndex

vector<size_t> m_speciesLocalPhaseIndex

Index that keeps track of the index of the species within the local phase.

This returns the local index of the species within the phase. Its argument is the global species index within the VCS problem.

k = m_speciesLocalPhaseIndex[kspec]

k varies between 0 and the nSpecies in the phase

Length = number of species

Definition at line 1321 of file vcs_solve.h.

◆ m_elementMapIndex

vector<size_t> m_elementMapIndex

Index vector that keeps track of the rearrangement of the elements.

At the end of each run, the element vector and associated data gets put back in the original order.

Example

e    = m_elementMapIndex[eNum]
eNum  = current order in the vcs_solve object
e     = original order in the MultiPhase object

Definition at line 1334 of file vcs_solve.h.

◆ m_indexRxnToSpecies

vector<size_t> m_indexRxnToSpecies

Mapping between the species index for noncomponent species and the full species index.

ir[irxn] = Mapping between the reaction index for noncomponent formation reaction of a species and the full species index.

Initially set to a value of K = NC + I This vector has length equal to number of noncomponent species in the mechanism. It starts with the first current noncomponent species in the mechanism. kspec = ir[irxn]

Definition at line 1347 of file vcs_solve.h.

◆ m_speciesStatus

vector<int> m_speciesStatus

Major -Minor status vector for the species in the problem.

The index for this is species. The reaction that this is referring to is kspec = irxn + m_numComponents. For possible values and their meanings, see vcs_evaluate_speciesType().

Definition at line 1355 of file vcs_solve.h.

◆ m_phaseID

vector<size_t> m_phaseID

Mapping from the species number to the phase number.

Definition at line 1358 of file vcs_solve.h.

◆ m_SSPhase

vector<char> m_SSPhase

Boolean indicating whether a species belongs to a single-species phase.

Definition at line 1362 of file vcs_solve.h.

◆ m_speciesName

vector<string> m_speciesName

Species string name for the kth species.

Definition at line 1365 of file vcs_solve.h.

◆ m_elementName

vector<string> m_elementName

Vector of strings containing the element names.

ElName[j] = String containing element names

Definition at line 1371 of file vcs_solve.h.

◆ m_elType

vector<int> m_elType

Type of the element constraint.

0 - VCS_ELEM_TYPE_ABSPOS Normal element that is positive or zero in all species.
1 - VCS_ELEM_TYPE_ELECTRONCHARGE element dof that corresponds to the electronic charge DOF.
2 - VCS_ELEM_TYPE_CHARGENEUTRALITY element dof that corresponds to a required charge neutrality constraint on the phase. The element abundance is always exactly zero.
3 - VCS_ELEM_TYPE_OTHERCONSTRAINT Other constraint which may mean that a species has neg 0 or pos value of that constraint (other than charge)

Definition at line 1386 of file vcs_solve.h.

◆ m_elementActive

vector<int> m_elementActive

Specifies whether an element constraint is active.

The default is true. Length = nelements

Definition at line 1392 of file vcs_solve.h.

◆ m_VolPhaseList

vector<unique_ptr<vcs_VolPhase> > m_VolPhaseList

Array of Phase Structures. Length = number of phases.

Definition at line 1395 of file vcs_solve.h.

◆ m_actConventionSpecies

vector<int> m_actConventionSpecies

specifies the activity convention of the phase containing the species

0 = molar based
1 = molality based

length = number of species

Definition at line 1404 of file vcs_solve.h.

◆ m_phaseActConvention

vector<int> m_phaseActConvention

specifies the activity convention of the phase.

0 = molar based
1 = molality based

length = number of phases

Definition at line 1413 of file vcs_solve.h.

◆ m_lnMnaughtSpecies

vector<double> m_lnMnaughtSpecies

specifies the ln(Mnaught) used to calculate the chemical potentials

For molar based activity conventions this will be equal to 0.0. length = number of species.

Definition at line 1420 of file vcs_solve.h.

◆ m_actCoeffSpecies_new

vector<double> m_actCoeffSpecies_new

Molar-based Activity Coefficients for Species.

Length = number of species

Definition at line 1424 of file vcs_solve.h.

◆ m_actCoeffSpecies_old

vector<double> m_actCoeffSpecies_old

Molar-based Activity Coefficients for Species based on old mole numbers.

These activity coefficients are based on the m_molNumSpecies_old values Molar based activity coefficients. Length = number of species

Definition at line 1431 of file vcs_solve.h.

◆ m_np_dLnActCoeffdMolNum

Array2D m_np_dLnActCoeffdMolNum

Change in the log of the activity coefficient with respect to the mole number multiplied by the phase mole number.

size = nspecies x nspecies

This is a temporary array that gets regenerated every time it's needed. It is not swapped wrt species.

Definition at line 1441 of file vcs_solve.h.

◆ m_wtSpecies

vector<double> m_wtSpecies

Molecular weight of each species.

units = kg/kmol. length = number of species.

note: this is a candidate for removal. I don't think we use it.

Definition at line 1449 of file vcs_solve.h.

◆ m_chargeSpecies

vector<double> m_chargeSpecies

Charge of each species. Length = number of species.

Definition at line 1452 of file vcs_solve.h.

◆ m_speciesThermoList

vector<unique_ptr<VCS_SPECIES_THERMO> > m_speciesThermoList

Vector of pointers to thermo structures which identify the model and parameters for evaluating the thermodynamic functions for that particular species.

SpeciesThermo[k] pointer to the thermo information for the kth species

Definition at line 1462 of file vcs_solve.h.

◆ m_useActCoeffJac

int m_useActCoeffJac = 0

Choice of Hessians.

If this is true, then we will use a better approximation to the Hessian based on Jacobian of the ln(ActCoeff) with respect to mole numbers

Definition at line 1469 of file vcs_solve.h.

◆ m_totalVol

double m_totalVol

Total volume of all phases. Units are m^3.

Definition at line 1472 of file vcs_solve.h.

◆ m_PMVolumeSpecies

vector<double> m_PMVolumeSpecies

Partial molar volumes of the species.

units = mks (m^3/kmol) Length = number of species

Definition at line 1479 of file vcs_solve.h.

◆ m_Faraday_dim

double m_Faraday_dim

dimensionless value of Faraday's constant, F / RT (1/volt)

Definition at line 1482 of file vcs_solve.h.

◆ m_VCount

VCS_COUNTERS* m_VCount = nullptr

Timing and iteration counters for the vcs object.

Definition at line 1485 of file vcs_solve.h.

◆ m_debug_print_lvl

int m_debug_print_lvl = 0

Debug printing lvl.

Levels correspond to the following guidelines

0 No printing at all
1 Serious warnings or fatal errors get one line
2 one line per each successful vcs package call
3 one line per every successful solve_TP calculation
4 one line for every successful operation -> solve_TP gets a summary report
5 each iteration in solve_TP gets a report with one line per species
6 Each decision in solve_TP gets a line per species in addition to 4
10 Additionally Hessian matrix is printed out

Definition at line 1499 of file vcs_solve.h.

◆ m_timing_print_lvl

int m_timing_print_lvl = 1

printing level of timing information

1 allowing printing of timing
0 do not allow printing of timing -> everything is printed as a NA.

Definition at line 1506 of file vcs_solve.h.

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

Detailed Description

Public Member Functions

Static Public Member Functions

Public Attributes

Private Member Functions

Private Attributes

Friends

Constructor & Destructor Documentation

◆ VCS_SOLVE()

Member Function Documentation

◆ vcs()

◆ vcs_solve_TP()

◆ vcs_reinsert_deleted()

◆ vcs_basopt()

Internal Variables calculated by this routine:

◆ vcs_basisOptMax()

◆ vcs_species_type()

◆ vcs_evaluate_speciesType()

◆ vcs_dfe()

Handling of Small Species:

Handling of "Species" Representing Interfacial Voltages

◆ vcs_updateVP()

◆ vcs_popPhasePossible()

◆ vcs_popPhaseID()

◆ vcs_popPhaseRxnStepSizes()

◆ vcs_RxnStepSizes()

Output

◆ vcs_tmoles()

◆ vcs_deltag()

◆ vcs_switch_pos()

◆ vcs_phaseStabilityTest()

◆ vcs_TP()

◆ vcs_evalSS_TP()

◆ vcs_fePrep_TP()

◆ vcs_VolTotal()

◆ vcs_prep()

◆ vcs_elem_rearrange()

◆ vcs_switch_elem_pos()

◆ vcs_Hessian_diag_adj()

◆ vcs_Hessian_actCoeff_diag()

◆ vcs_CalcLnActCoeffJac()

◆ vcs_report()

◆ vcs_elab()

◆ vcs_elabcheck()

◆ vcs_elabPhase()

◆ vcs_elcorr()

◆ vcs_inest_TP()

◆ vcs_setMolesLinProg()

◆ vcs_Total_Gibbs()

◆ vcs_GibbsPhase()

◆ vcs_prob_update()

◆ vcs_prob_specifyFully()

◆ vcs_zero_species()

◆ vcs_delete_species()

◆ vcs_delete_multiphase()

◆ delta_species()

◆ vcs_add_all_deleted()

◆ vcs_recheck_deleted()

◆ vcs_minor_alt_calc()

◆ vcs_globStepDamp()

◆ l2normdg()

◆ vcs_inest()

◆ vcs_SSPhase()

◆ vcs_delete_memory()

◆ vcs_counters_init()

◆ vcs_TCounters_report()

◆ vcs_updateMolNumVolPhases()

◆ prob_report()

◆ addPhaseElements()

◆ addOnePhaseSpecies()

◆ addElement()

◆ disableTiming()

Member Data Documentation

◆ m_printLvl

◆ m_nsp

◆ m_nelem

◆ m_numComponents

◆ m_numRxnTot

◆ m_numSpeciesRdc

◆ m_numRxnRdc