Cantera  2.2.1
VCS_SOLVE Class Reference

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>

Collaboration diagram for VCS_SOLVE:
[legend]

## Public Member Functions

void vcs_initSizes (const size_t nspecies0, const size_t nelements, const size_t nphase0)
Initialize the sizes within the VCS_SOLVE object. More...

int vcs (VCS_PROB *vprob, int ifunc, 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...

int vcs_PS (VCS_PROB *vprob, int iph, int printLvl, double &feStable)

void vcs_reinsert_deleted (size_t kspec)

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_chemPotPhase (const int stateCalc, const size_t iph, const double *const molNum, double *const ac, double *const mu_i, const bool do_deleted=false)
We calculate the dimensionless chemical potentials of all species in a single phase. 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_printSpeciesChemPot (const int stateCalc) const
Print out a table of chemical potentials. 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...

int vcs_phasePopDeterminePossibleList ()
Determine the list of problems that need to be checked to see if there are any phases pops. More...

size_t vcs_popPhaseID (std::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_deltag_Phase (const size_t iphase, const bool doDeleted, const int stateCalc, const bool alterZeroedPhases=true)
Calculate deltag of formation for all species in a single phase. More...

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_birthGuess (const int kspec)
Birth guess returns the number of moles of a species that is coming back to life. More...

int vcs_solve_phaseStability (const int iphase, int ifunc, double &funcval, int print_lvl)
Routine that independently determines whether a phase should be popped under the current conditions. 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)

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

int vcs_prep ()
Prepare the object for solution. More...

bool vcs_wellPosed (VCS_PROB *vprob)
In this routine, we check for things that will cause the algorithm to fail. 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...

Calculates reaction adjustments using a full Hessian approximation. 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...

double vcs_line_search (const size_t irxn, const double dx_orig, char *const ANOTE=0)
A line search algorithm is carried out on one reaction. More...

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

int vcs_rearrange ()
Switch all species data back to the original order. More...

double vcs_nondim_Farad (int mu_units, double TKelvin) const
Returns the multiplier for electric charge terms. More...

double vcs_nondimMult_TP (int mu_units, double TKelvin) const
Returns the multiplier for the nondimensionalization of the equations. More...

void vcs_nondim_TP ()
Nondimensionalize the problem data. More...

void vcs_redim_TP ()
Redimensionalize the problem data. More...

void vcs_printChemPotUnits (int unitsFormat) const
Print the string representing the Chemical potential units. More...

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

bool vcs_elabcheck (int ibound)

void vcs_elabPhase (size_t iphase, double *const elemAbundPhase)

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

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...

int vcs_prob_update (VCS_PROB *pub)
Transfer the results of the equilibrium calculation back to VCS_PROB. More...

int vcs_prob_specifyFully (const VCS_PROB *pub)
Fully specify the problem to be solved using VCS_PROB. More...

int vcs_prob_specify (const VCS_PROB *pub)
Specify the problem to be solved using VCS_PROB, incrementally. More...

int vcs_rank (const double *awtmp, size_t numSpecies, const double *matrix, size_t numElemConstraints, std::vector< size_t > &compRes, std::vector< size_t > &elemComp, int *const usedZeroedSpecies) const
Calculate the rank of a matrix and return the rows and columns that will generate an independent basis for that rank. More...

## Public Attributes

size_t NSPECIES0
value of the number of species used to malloc data structures More...

size_t NPHASE0
value of the number of phases used to malloc data structures More...

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

size_t m_numElemConstraints
Number of element constraints in the problem. More...

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

size_t m_numRxnTot
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
Current number of non-component species in the problem. More...

size_t m_numRxnMinorZeroed
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...

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

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

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

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

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

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

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

std::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...

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

double m_temperature
Temperature (Kelvin) More...

double m_pressurePA
Pressure (units are determined by m_VCS_UnitsFormat. More...

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

double m_tolmaj
Tolerance requirement for major species. More...

double m_tolmin
Tolerance requirements for minor species. More...

double m_tolmaj2
Below this, major species aren't refined any more. More...

double m_tolmin2
Below this, minor species aren't refined any more. More...

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

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

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

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

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

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

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

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

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

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

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

std::vector< vcs_VolPhase * > m_VolPhaseList
Array of Phase Structures. Length = number of phases. More...

std::string m_title
String containing the title of the run. More...

char m_unitsState
This specifies the current state of units for the Gibbs free energy properties in the program. More...

double m_totalMoleScale
Multiplier for the mole numbers within the nondimensionless formulation. More...

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

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

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

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

std::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...

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

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

std::vector< std::vector
< size_t > >
phasePopProblemLists_

std::vector< VCS_SPECIES_THERMO * > m_speciesThermoList
Vector of pointers to thermostructures which identify the model and parameters for evaluating the thermodynamic functions for that particular species. More...

int m_useActCoeffJac
Choice of Hessians. More...

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

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

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

VCS_COUNTERSm_VCount
Timing and iteration counters for the vcs object. More...

int m_debug_print_lvl
Debug printing lvl. More...

int m_timing_print_lvl
printing level of timing information More...

int m_VCS_UnitsFormat
Units for the chemical potential data. 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...

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...

bool recheck_deleted_phase (const int iphase)
Recheck deletion condition for 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 prneav () const
Print out and check the elemental abundance 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 (void)
Calculate the status of single species phases. More...

double deltaG_Recalc_Rxn (const int stateCalc, const size_t irxn, const double *const molNum, double *const ac, double *const mu_i)
This function recalculates the deltaG for reaction, irxn. 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

std::vector< double > m_sm

std::vector< double > m_ss

std::vector< double > m_sa

std::vector< double > m_aw

std::vector< double > m_wx

## Friends

class vcs_phaseStabilitySolve

## 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 49 of file vcs_solve.h.

## Member Function Documentation

 void vcs_initSizes ( const size_t nspecies0, const size_t nelements, const size_t nphase0 )

Initialize the sizes within the VCS_SOLVE object.

This resizes all of the internal arrays within the object. This routine operates in two modes. If all of the parameters are the same as it currently exists in the object, nothing is done by this routine; a quick exit is carried out and all of the data in the object persists.

If any of the parameters are different than currently exists in the object, then all of the data in the object must be redone. It may not be zeroed, but it must be redone.

Parameters
 nspecies0 Number of species within the object nelements Number of element constraints within the problem nphase0 Number of phases defined within the problem.

Definition at line 59 of file vcs_solve.cpp.

 int vcs ( VCS_PROB * vprob, int ifunc, int ipr, int ip1, int maxit )

Solve an equilibrium problem.

This is the main interface routine to the equilibrium solver

Input:

Parameters
 vprob Object containing the equilibrium Problem statement ifunc Determines the operation to be done: Valid values: 0 -> Solve a new problem by initializing structures first. An initial estimate may or may not have been already determined. This is indicated in the VCS_PROB structure. 1 -> The problem has already been initialized and set up. We call this routine to resolve it using the problem statement and solution estimate contained in the VCS_PROB structure. 2 -> Don't solve a problem. Destroy all the private structures. 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

Output:

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

Definition at line 244 of file vcs_solve.cpp.

Referenced by vcs_MultiPhaseEquil::equilibrate_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.

Referenced by VCS_SOLVE::vcs_TP().

 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 1959 of file vcs_solve_TP.cpp.

Referenced by VCS_SOLVE::vcs_elcorr().

 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 (nc*ne in length) sm[i+j*ne] [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
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 2512 of file vcs_solve_TP.cpp.

Referenced by VCS_SOLVE::vcs_inest(), and VCS_SOLVE::vcs_prep_oneTime().

 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 3067 of file vcs_solve_TP.cpp.

 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
Returns the calculated species type

Definition at line 3122 of file vcs_solve_TP.cpp.

 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 3804 of file vcs_solve_TP.cpp.

 void vcs_chemPotPhase ( const int stateCalc, const size_t iph, const double *const molNum, double *const ac, double *const mu_i, const bool do_deleted = false )

We calculate the dimensionless chemical potentials of all species in a single phase.

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.

# Formula:

## Ideal Mixtures:

 m_feSpecies(I) = m_SSfeSpecies(I) + ln(z(I)) - ln(m_tPhaseMoles[iph])
+ m_chargeSpecies[I] * Faraday_dim * m_phasePhi[iphase];


(This is equivalent to the adding the log of the mole fraction onto the standard chemical potential. )

## Non-Ideal Mixtures:

### ActivityConvention = 0: molarity activity formulation

m_feSpecies(I) = m_SSfeSpecies(I)
+ ln(ActCoeff[I] * z(I)) - ln(m_tPhaseMoles[iph])
+ m_chargeSpecies[I] * Faraday_dim * m_phasePhi[iphase];


( This is equivalent to the adding the log of the mole fraction multiplied by the activity coefficient onto the standard chemical potential. )

### ActivityConvention = 1: molality activity formulation

m_feSpecies(I) = m_SSfeSpecies(I)
+ ln(ActCoeff[I] * z(I)) - ln(m_tPhaseMoles[iph])
- ln(Mnaught * m_units)
+ m_chargeSpecies[I] * Faraday_dim * m_phasePhi[iphase];


Note: m_SSfeSpecies(I) is the molality based standard state. However, ActCoeff[I] is the molar based activity coefficient We have used the formulas:

ActCoeff_M[I] =  ActCoeff[I] / Xmol[N]


where Xmol[N] is the mole fraction of the solvent and ActCoeff_M[I] is the molality based act coeff.

Note: This is equivalent to the "normal" molality formulation:

m_feSpecies(I) = m_SSfeSpecies(I)
+ ln(ActCoeff_M[I] * m(I))
+ m_chargeSpecies[I] * Faraday_dim * m_phasePhi[iphase]


where m[I] is the molality of the ith solute

m[I] = Xmol[I] / ( Xmol[N] * Mnaught * m_units)


z(I)/tPhMoles_ptr[iph] = Xmol[i] is the mole fraction of i in the phase.

NOTE: As per the discussion in vcs_dfe(), for small species where the mole fraction is small:

z(i) < VCS_DELETE_MINORSPECIES_CUTOFF


The chemical potential is calculated as:

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

Parameters
 [in] iph Phase to be calculated [in] molNum Number of moles of species i (VCS species order) [out] ac Activity coefficients for species in phase (VCS species order) [out] mu_i Dimensionless chemical potentials for phase species (VCS species order)

Definition at line 3315 of file vcs_solve_TP.cpp.

Referenced by VCS_SOLVE::deltaG_Recalc_Rxn().

 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, i.e., 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 3366 of file vcs_solve_TP.cpp.

Referenced by VCS_SOLVE::vcs_inest(), and VCS_SOLVE::vcs_report().

 void vcs_printSpeciesChemPot ( const int stateCalc ) const

Print out a table of chemical potentials.

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 3604 of file vcs_solve_TP.cpp.

 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 3785 of file vcs_solve_TP.cpp.

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

Definition at line 16 of file vcs_phaseStability.cpp.

 int vcs_phasePopDeterminePossibleList ( )

Determine the list of problems that need to be checked to see if there are any phases pops.

This routine evaluates and fills in #phasePopProblemLists_. Need to work in species that are zeroed by element constraints.

Returns
Returns the number of problems that must be checked.

Definition at line 110 of file vcs_phaseStability.cpp.

 size_t vcs_popPhaseID ( std::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
returns the phase id of the phase that pops back into existence. Returns -1 if there are no phases

Definition at line 228 of file vcs_phaseStability.cpp.

 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
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 341 of file vcs_phaseStability.cpp.

 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.

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

Definition at line 20 of file vcs_rxnadj.cpp.

 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 3736 of file vcs_solve_TP.cpp.

References vcs_VolPhase::setTotalMoles(), and VCS_SPECIES_TYPE_MOLNUM.

 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 3877 of file vcs_solve_TP.cpp.

Referenced by VCS_SOLVE::vcs_inest().

 void vcs_deltag_Phase ( const size_t iphase, const bool doDeleted, const int stateCalc, const bool alterZeroedPhases = true )

Calculate deltag of formation for all species in a single phase.

Calculate deltag of formation for all species in a single phase. It is assumed that the fe[] is up to date for all species. However, if the phase is currently zeroed out, a subproblem is calculated to solve for AC[i] and pseudo-X[i] for that phase.

Parameters
 iphase phase index of the phase to be calculated doDeleted boolean indicating whether to do deleted species or not stateCalc integer describing which set of free energies to use and where to stick the results. alterZeroedPhases boolean indicating whether we should add in a special section for zeroed phases.

NOTE: this is currently not used used anywhere. It may be in the future?

Definition at line 4206 of file vcs_solve_TP.cpp.

 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 4335 of file vcs_solve_TP.cpp.

Referenced by VCS_SOLVE::vcs_rearrange().

 double vcs_birthGuess ( const int kspec )

Birth guess returns the number of moles of a species that is coming back to life.

Birth guess returns the number of moles of a species that is coming back to life. Note, this routine is not applicable if the whole phase is coming back to life, not just one species in that phase.

Do a minor alt calculation. But, cap the mole numbers at 1.0E-15. For SS phases use VCS_DELETE_SPECIES_CUTOFF * 100.

The routine makes sure the guess doesn't reduce the concentration of a component by more than 1/3. Note this may mean that the vlaue coming back from this routine is zero or a very small number.

Parameters
 kspec Species number that is coming back to life
Returns
Returns the number of kmol that the species should have.

Definition at line 4423 of file vcs_solve_TP.cpp.

 int vcs_solve_phaseStability ( const int iphase, int ifunc, double & funcval, int print_lvl )

Routine that independently determines whether a phase should be popped under the current conditions.

Definition at line 139 of file vcs_solve_phaseStability.cpp.

References VCS_DATA_PTR, and VCS_STATECALC_OLD.

 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 504 of file vcs_phaseStability.cpp.

 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 nondimensionalize the system 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 (units given by m_VCS_UnitsFormat variable
Returns
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 7 of file vcs_TP.cpp.

 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 58 of file vcs_TP.cpp.

Referenced by VCS_SOLVE::vcs_prep_oneTime(), and VCS_SOLVE::vcs_TP().

 void vcs_fePrep_TP ( void )

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 85 of file vcs_TP.cpp.

Referenced by VCS_SOLVE::vcs_TP().

 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 return value is the total volume of the entire system in units of m**3.

Definition at line 983 of file vcs_solve.cpp.

Referenced by VCS_SOLVE::vcs_report().

 int vcs_prep_oneTime ( 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.

This routine is always followed by vcs_prep(). Therefore, tasks that need to be done for every call to vcsc() should be placed in vcs_prep() and not in this routine.

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.

1. Fill in the SSPhase[] array.
2. 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.
3. 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.
Parameters
 printLvl Print level of the routine
Returns
VCS_SUCCESS = everything went OK

Definition at line 60 of file vcs_prep.cpp.

 int vcs_prep ( )

Prepare the object for solution.

This routine is mostly concerned with changing the private data to be consistent with that needed for solution. It is called for every invocation of the vcs_solve() except for the cleanup invocation.

1. Initialization of arrays to zero.
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 206 of file vcs_prep.cpp.

 bool vcs_wellPosed ( VCS_PROB * vprob )

In this routine, we check for things that will cause the algorithm to fail.

We check to see if the problem is well posed. If it is not, we return false and print out error conditions.

Current there is one condition. If all the element abundances are zero, the algorithm will fail.

Parameters
 vprob VCS_PROB pointer to the definition of the equilibrium problem
Returns
If true, the problem is well-posed. If false, the problem is not well posed.

Definition at line 225 of file vcs_prep.cpp.

References VCS_PROB::gai, VCS_PROB::ne, and plogf.

 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 20 of file vcs_elem_rearrange.cpp.

Referenced by VCS_SOLVE::vcs_prep_oneTime().

 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 174 of file vcs_elem_rearrange.cpp.

Referenced by VCS_SOLVE::vcs_elem_rearrange().

Calculates reaction adjustments using a full Hessian approximation.

This does what equation 6.4-16, p. 143 in Smith and Missen is supposed to do. However, a full matrix is formed and then solved via a conjugate gradient algorithm. No preconditioning is done.

If special branching is warranted, then the program bails out.

## Output

DS(I) : reaction adjustment, where I refers to the Ith species Special branching occurs sometimes. This causes the component basis to be reevaluated return = 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.

Special attention is taken to flag cases where the direction of the update is contrary to the steepest descent rule. This is an important attribute of the regular vcs algorithm. We don't want to violate this.

NOTE: currently this routine is not used.

Definition at line 368 of file vcs_rxnadj.cpp.

 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.

NOTE: currently this routine is not used

Definition at line 576 of file vcs_rxnadj.cpp.

References VCS_SOLVE::vcs_Hessian_actCoeff_diag().

Referenced by VCS_SOLVE::vcs_RxnStepSizes().

 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)

NOTE: currently this routine is not used

Definition at line 594 of file vcs_rxnadj.cpp.

 void vcs_CalcLnActCoeffJac ( const double *const moleSpeciesVCS )

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

Definition at line 627 of file vcs_rxnadj.cpp.

Referenced by VCS_SOLVE::vcs_RxnStepSizes().

 double vcs_line_search ( const size_t irxn, const double dx_orig, char *const ANOTE = 0 )

A line search algorithm is carried out on one reaction.

In this routine we carry out a rough line search algorithm to make sure that the m_deltaGRxn_new doesn't switch signs prematurely.

Parameters
 irxn Reaction number dx_orig Original step length ANOTE Output character string stating the conclusions of the line search
Returns
Returns the optimized step length found by the search

Definition at line 668 of file vcs_rxnadj.cpp.

 int vcs_report ( int iconv )
 int vcs_rearrange ( )

Switch all species data back to the original order.

This destroys the data based on reaction ordering.

Definition at line 15 of file vcs_rearrange.cpp.

 double vcs_nondim_Farad ( int mu_units, double TKelvin ) const

Returns the multiplier for electric charge terms.

Definition at line 18 of file vcs_nondim.cpp.

Referenced by VCS_SOLVE::vcs_nondim_TP().

 double vcs_nondimMult_TP ( int mu_units, double TKelvin ) const

Returns the multiplier for the nondimensionalization of the equations.

This is basically equal to RT

Parameters
 mu_units integer representing the dimensional units system TKelvin double Temperature in Kelvin
Returns
Returns the value of RT

Definition at line 38 of file vcs_nondim.cpp.

References Cantera::GasConst_cal_mol_K, Cantera::GasConstant, and Cantera::int2str().

Referenced by VCS_SOLVE::vcs_nondim_TP(), VCS_SOLVE::vcs_redim_TP(), and VCS_SOLVE::vcs_report().

 void vcs_nondim_TP ( )

Nondimensionalize the problem data.

Nondimensionalize the free energies using the divisor, R * T

Essentially the internal data can either be in dimensional form or in nondimensional form. This routine switches the data from dimensional form into nondimensional form.

Todo:
Add a scale factor based on the total mole numbers. The algorithm contains hard coded numbers based on the total mole number. If we ever were faced with a problem with significantly different total kmol numbers than one the algorithm would have problems.

Definition at line 60 of file vcs_nondim.cpp.

Referenced by VCS_SOLVE::vcs_report(), and VCS_SOLVE::vcs_TP().

 void vcs_redim_TP ( void )

Redimensionalize the problem data.

Reddimensionalize the free energies using the multiplier R * T

Essentially the internal data can either be in dimensional form or in nondimensional form. This routine switches the data from nondimensional form into dimensional form.

Definition at line 145 of file vcs_nondim.cpp.

Referenced by VCS_SOLVE::vcs_report(), and VCS_SOLVE::vcs_TP().

 void vcs_printChemPotUnits ( int unitsFormat ) const

Print the string representing the Chemical potential units.

This gets printed using plogf()

Parameters
 unitsFormat Integer representing the units system

Definition at line 189 of file vcs_nondim.cpp.

References plogf.

Referenced by VCS_SOLVE::vcs_report().

 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 13 of file vcs_elem.cpp.

Referenced by VCS_SOLVE::vcs_elcorr(), and VCS_SOLVE::vcs_inest_TP().

 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 25 of file vcs_elem.cpp.

Referenced by VCS_SOLVE::vcs_elcorr(), and VCS_SOLVE::vcs_inest_TP().

 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 89 of file vcs_elem.cpp.

Referenced by VCS_SOLVE::vcs_report().

 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 103 of file vcs_elem.cpp.

Referenced by VCS_SOLVE::vcs_inest_TP().

 int vcs_inest_TP ( )

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

Returns
Return value indicates success:
• 0: successful initial guess
• -1: Unsuccessful initial guess; the elemental abundances aren't satisfied.

Definition at line 320 of file vcs_inest.cpp.

Referenced by VCS_SOLVE::vcs_TP().

 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 32 of file vcs_setMolesLinProg.cpp.

References plogf, VCS_DATA_PTR, VCS_SPECIES_INTERFACIALVOLTAGE, and VCS_SUCCESS.

Referenced by VCS_SOLVE::vcs_inest().

 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 16 of file vcs_Gibbs.cpp.

Referenced by VCS_SOLVE::vcs_inest_TP(), and VCS_SOLVE::vcs_report().

 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 41 of file vcs_Gibbs.cpp.

Referenced by VCS_SOLVE::vcs_report().

 int vcs_prob_update ( VCS_PROB * pub )

Transfer the results of the equilibrium calculation back to VCS_PROB.

The VCS_PROB structure is returned to the user.

Parameters
 pub Pointer to VCS_PROB object that will get the results of the equilibrium calculation transfered to it.

Definition at line 880 of file vcs_solve.cpp.

 int vcs_prob_specifyFully ( const VCS_PROB * pub )

Fully specify the problem to be solved using VCS_PROB.

Use the contents of the VCS_PROB to specify the contents of the private data, VCS_SOLVE.

Parameters
 pub Pointer to VCS_PROB that will be used to initialize the current equilibrium problem

Definition at line 375 of file vcs_solve.cpp.

 int vcs_prob_specify ( const VCS_PROB * pub )

Specify the problem to be solved using VCS_PROB, incrementally.

Use the contents of the VCS_PROB to specify the contents of the private data, VCS_SOLVE.

It's assumed we are solving the same problem.

Parameters
 pub Pointer to VCS_PROB that will be used to initialize the current equilibrium problem

Definition at line 756 of file vcs_solve.cpp.

 int vcs_zero_species ( const size_t kspec )
private

Zero out the concentration of a species.

Make sure to conserveelements 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 1861 of file vcs_solve_TP.cpp.

References plogendl, plogf, and VCS_SPECIES_TYPE_INTERFACIALVOLTAGE.

 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 1882 of file vcs_solve_TP.cpp.

 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
Returns whether the operation was successful or not

Definition at line 2019 of file vcs_solve_TP.cpp.

 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 1805 of file vcs_solve_TP.cpp.

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 2289 of file vcs_solve_TP.cpp.

 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 + log((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 2172 of file vcs_solve_TP.cpp.

References plogf, VCS_DATA_PTR, VCS_RELDELETE_SPECIES_CUTOFF, and VCS_STATECALC_NEW.

 bool recheck_deleted_phase ( const int iphase )
private

Recheck deletion condition for multispecies phases.

We assume here that DG_i_0 has been calculated for deleted species correctly

m_feSpecies(I) = m_SSfeSpecies(I)
+ ln(ActCoeff[I])
- ln(Mnaught * m_units)
+ m_chargeSpecies[I] * Faraday_dim * m_phasePhi[iphase];

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

DG_i_0 =  m_feSpecies(I) - sum_m{ a_i_m  DG_m }


by first evaluating:

DG_i_O = u_i_O - sum_u.


Then, the phase pops into existence iff

phaseDG = 1.0 - sum_i{exp(-DG_i_O)}  < 0.0


This formula works for both single species phases and for multispecies phases. It's an overkill for single species phases.

Parameters
 iphase Phase index number
Returns
Returns true if the phase is currently deleted but should be reinstated. Returns false otherwise.

NOTE: this routine is currently not used in the code, and contains some basic changes that are incompatible.

assumptions:

1. Vphase Existence is up to date
2. Vphase->IndSpecies is up to date
3. m_deltaGRxn_old[irxn] is up to date

Definition at line 2255 of file vcs_solve_TP.cpp.

 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.

Definition at line 1703 of file vcs_solve_TP.cpp.

 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 (i.e., 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 2389 of file vcs_solve_TP.cpp.

 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 3718 of file vcs_solve_TP.cpp.

References VCS_SPECIES_MAJOR, VCS_SPECIES_MINOR, and VCS_SPECIES_ZEROEDMS.

 void prneav ( ) const
private

Print out and check the elemental abundance vector.

Definition at line 3680 of file vcs_solve_TP.cpp.

References plogendl, plogf, and VCS_SPECIES_TYPE_INTERFACIALVOLTAGE.

 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.

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+j*ne] = QR matrix work space (ne*ne in length) ss ss[j] = Gram-Schmidt orthog work space (ne in length) test This is a small negative number.

Definition at line 21 of file vcs_inest.cpp.

Referenced by VCS_SOLVE::vcs_inest_TP().

 void vcs_SSPhase ( void )
private

Calculate the status of single species phases.

Definition at line 18 of file vcs_prep.cpp.

Referenced by VCS_SOLVE::vcs_prep_oneTime().

 double deltaG_Recalc_Rxn ( const int stateCalc, const size_t irxn, const double *const molNum, double *const ac, double *const mu_i )
private

This function recalculates the deltaG for reaction, irxn.

This function recalculates the deltaG for reaction irxn, given the mole numbers in molNum. It uses the temporary space mu_i, to hold the recalculated chemical potentials. It only recalculates the chemical potentials for species in phases which participate in the irxn reaction. This function is used by the vcs_line_search algorithm() and should not be used widely due to the unknown state it leaves the system.

Parameters
 [in] irxn Reaction number [in] molNum Current mole numbers of species to be used as input to the calculation (units = kmol), (length = totalNuMSpecies) [out] ac Activity coefficients (length = totalNumSpecies) Note this is only partially formed. Only species in phases that participate in the reaction will be updated [out] mu_i dimensionless chemical potentials (length totalNumSpecies) Note this is only partially formed. Only species in phases that participate in the reaction will be updated
Returns
Returns the dimensionless deltaG of the reaction

Definition at line 652 of file vcs_rxnadj.cpp.

Referenced by VCS_SOLVE::vcs_line_search().

 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 221 of file vcs_solve.cpp.

 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 965 of file vcs_solve.cpp.

 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 373 of file vcs_report.cpp.

 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 4506 of file vcs_solve_TP.cpp.

 int vcs_rank ( const double * awtmp, size_t numSpecies, const double * matrix, size_t numElemConstraints, std::vector< size_t > & compRes, std::vector< size_t > & elemComp, int *const usedZeroedSpecies ) const

Calculate the rank of a matrix and return the rows and columns that will generate an independent basis for that rank.

Definition at line 38 of file vcs_rank.cpp.

References plogendl, plogf, VCS_DATA_PTR, and Cantera::warn_deprecated().

## Member Data Documentation

 size_t NSPECIES0

value of the number of species used to malloc data structures

Definition at line 1487 of file vcs_solve.h.

 size_t NPHASE0

value of the number of phases used to malloc data structures

Definition at line 1490 of file vcs_solve.h.

 size_t m_numSpeciesTot

Total number of species in the problems.

Definition at line 1493 of file vcs_solve.h.

 size_t m_numElemConstraints

Number of element constraints in the problem.

This is typically equal to the number of elements in the problem

Definition at line 1499 of file vcs_solve.h.

 size_t m_numComponents

Number of components calculated for the problem.

Definition at line 1502 of file vcs_solve.h.

 size_t m_numRxnTot

Total number of non-component species in the problem.

Definition at line 1505 of file vcs_solve.h.

Referenced by VCS_SOLVE::vcs_inest(), VCS_SOLVE::vcs_prep_oneTime(), and VCS_SOLVE::vcs_report().

 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 1512 of file vcs_solve.h.

 size_t m_numRxnRdc

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 1519 of file vcs_solve.h.

 size_t m_numRxnMinorZeroed

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

Definition at line 1523 of file vcs_solve.h.

 size_t m_numPhases

Number of Phases in the problem.

Definition at line 1526 of file vcs_solve.h.

 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 1534 of file vcs_solve.h.

 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 multilplied 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 1552 of file vcs_solve.h.

 std::vector 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 1562 of file vcs_solve.h.

 std::vector 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 1569 of file vcs_solve.h.

Referenced by VCS_SOLVE::vcs_prep_oneTime().

 std::vector 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 1577 of file vcs_solve.h.

 std::vector 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 1584 of file vcs_solve.h.

 std::vector m_feSpecies_new

Dimensionless new free energy for all the species in the mechanism at the new tentatite 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 1593 of file vcs_solve.h.

 int m_doEstimateEquil

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 1605 of file vcs_solve.h.

Referenced by VCS_SOLVE::vcs_inest_TP(), VCS_SOLVE::vcs_prep_oneTime(), and VCS_SOLVE::vcs_TP().

 std::vector 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 1612 of file vcs_solve.h.

 std::vector 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 1625 of file vcs_solve.h.

 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 1632 of file vcs_solve.h.

 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 1636 of file vcs_solve.h.

Referenced by VCS_SOLVE::deltaG_Recalc_Rxn(), and VCS_SOLVE::vcs_prep().

 std::vector m_phasePhi

electric potential of the iph phase

Definition at line 1639 of file vcs_solve.h.

Referenced by VCS_SOLVE::vcs_report().

 std::vector m_molNumSpecies_new

Tentative value of the mole number vector.

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

Definition at line 1644 of file vcs_solve.h.

 std::vector 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 1654 of file vcs_solve.h.

 std::vector m_deltaGRxn_old

Last deltag[irxn] from the previous step.

Definition at line 1657 of file vcs_solve.h.

Referenced by VCS_SOLVE::vcs_nondim_TP(), and VCS_SOLVE::vcs_redim_TP().

 std::vector m_deltaGRxn_Deficient

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

Definition at line 1661 of file vcs_solve.h.

 std::vector m_deltaGRxn_tmp

Temporary vector of Rxn DeltaG's.

This is used from time to time, for printing purposes

Definition at line 1667 of file vcs_solve.h.

 std::vector 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 1674 of file vcs_solve.h.

Referenced by VCS_SOLVE::vcs_inest(), VCS_SOLVE::vcs_rxn_adj_cg(), and VCS_SOLVE::vcs_RxnStepSizes().

 std::vector 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 1686 of file vcs_solve.h.

 std::vector 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 1695 of file vcs_solve.h.

 double m_totalMolNum

Total number of kmoles in all phases.

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

Definition at line 1702 of file vcs_solve.h.

Referenced by VCS_SOLVE::vcs_RxnStepSizes().

 std::vector 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 1710 of file vcs_solve.h.

 std::vector 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 1719 of file vcs_solve.h.

Referenced by VCS_SOLVE::vcs_inest(), and VCS_SOLVE::vcs_prep().

 std::vector m_TmpPhase
mutable

Temporary vector of length NPhase.

Definition at line 1722 of file vcs_solve.h.

Referenced by VCS_SOLVE::vcs_inest().

 std::vector m_TmpPhase2
mutable

Temporary vector of length NPhase.

Definition at line 1725 of file vcs_solve.h.

Referenced by VCS_SOLVE::vcs_inest().

 std::vector m_deltaPhaseMoles

Change in the total moles in each phase.

Length number of phases.

Definition at line 1731 of file vcs_solve.h.

Referenced by VCS_SOLVE::vcs_inest(), and VCS_SOLVE::vcs_prep().

 double m_temperature

Temperature (Kelvin)

Definition at line 1734 of file vcs_solve.h.

 double m_pressurePA

Pressure (units are determined by m_VCS_UnitsFormat.

Values units
-1: atm
0: atm
1: atm
2: atm
3: Pa

Units being changed to Pa

Definition at line 1748 of file vcs_solve.h.

 std::vector 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 1755 of file vcs_solve.h.

 double m_tolmaj

Tolerance requirement for major species.

Definition at line 1758 of file vcs_solve.h.

 double m_tolmin

Tolerance requirements for minor species.

Definition at line 1761 of file vcs_solve.h.

 double m_tolmaj2

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

Definition at line 1764 of file vcs_solve.h.

 double m_tolmin2

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

Definition at line 1767 of file vcs_solve.h.

 std::vector 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 vcs_prob object and in the MultiPhase object

Definition at line 1781 of file vcs_solve.h.

 std::vector 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 1795 of file vcs_solve.h.

Referenced by VCS_SOLVE::vcs_prep_oneTime().

 std::vector 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 vcs_prob object and in the MultiPhase object

Definition at line 1808 of file vcs_solve.h.

Referenced by VCS_SOLVE::vcs_switch_elem_pos().

 std::vector 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 1821 of file vcs_solve.h.

 std::vector 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 1829 of file vcs_solve.h.

Referenced by VCS_SOLVE::vcs_elcorr(), VCS_SOLVE::vcs_rxn_adj_cg(), and VCS_SOLVE::vcs_RxnStepSizes().

 std::vector m_phaseID

Mapping from the species number to the phase number.

Definition at line 1832 of file vcs_solve.h.

 std::vector m_SSPhase

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

Definition at line 1836 of file vcs_solve.h.

 std::vector m_speciesName

Species string name for the kth species.

Definition at line 1839 of file vcs_solve.h.

 std::vector m_elementName

Vector of strings containing the element names.

ElName[j] = String containing element names

Definition at line 1845 of file vcs_solve.h.

 std::vector m_elType

Type of the element constraint.

Definition at line 1860 of file vcs_solve.h.

 std::vector m_elementActive

Specifies whether an element constraint is active.

The default is true. Length = nelements

Definition at line 1866 of file vcs_solve.h.

 std::vector m_VolPhaseList

Array of Phase Structures. Length = number of phases.

Definition at line 1869 of file vcs_solve.h.

 std::string m_title

String containing the title of the run.

Definition at line 1872 of file vcs_solve.h.

 char m_unitsState

This specifies the current state of units for the Gibbs free energy properties in the program.

The default is to have this unitless

Definition at line 1879 of file vcs_solve.h.

Referenced by VCS_SOLVE::vcs_nondim_TP(), VCS_SOLVE::vcs_redim_TP(), and VCS_SOLVE::vcs_report().

 double m_totalMoleScale

Multiplier for the mole numbers within the nondimensionless formulation.

All numbers within the main routine are on an absolute basis. This presents some problems wrt very large and very small mole numbers. We get around this by using a multiplier coming into and coming out of the equilibrium routines

Definition at line 1888 of file vcs_solve.h.

Referenced by VCS_SOLVE::vcs_nondim_TP(), VCS_SOLVE::vcs_redim_TP(), and VCS_SOLVE::vcs_report().

 std::vector 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 1897 of file vcs_solve.h.

 std::vector m_phaseActConvention

specifies the activity convention of the phase.

• 0 = molar based
• 1 = molality based

length = number of phases

Definition at line 1906 of file vcs_solve.h.

 std::vector 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 1913 of file vcs_solve.h.

Referenced by VCS_SOLVE::vcs_report().

 std::vector m_actCoeffSpecies_new

Molar-based Activity Coefficients for Species.

Length = number of species

Definition at line 1917 of file vcs_solve.h.

Referenced by VCS_SOLVE::vcs_line_search().

 std::vector 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 coeffients. Length = number of species

Definition at line 1924 of file vcs_solve.h.

Referenced by VCS_SOLVE::vcs_line_search(), and VCS_SOLVE::vcs_report().

 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 1934 of file vcs_solve.h.

Referenced by VCS_SOLVE::vcs_CalcLnActCoeffJac(), and VCS_SOLVE::vcs_Hessian_actCoeff_diag().

 std::vector 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 1942 of file vcs_solve.h.

 std::vector m_chargeSpecies

Charge of each species. Length = number of species.

Definition at line 1945 of file vcs_solve.h.

Referenced by VCS_SOLVE::vcs_report().

 std::vector m_speciesThermoList

Vector of pointers to thermostructures 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 1955 of file vcs_solve.h.

 int m_useActCoeffJac

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 1963 of file vcs_solve.h.

Referenced by VCS_SOLVE::vcs_RxnStepSizes().

 double m_totalVol

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

Definition at line 1966 of file vcs_solve.h.

Referenced by VCS_SOLVE::vcs_report().

 std::vector m_PMVolumeSpecies

Partial molar volumes of the species.

units = mks (m^3/kmol) -determined by m_VCS_UnitsFormat Length = number of species

Definition at line 1973 of file vcs_solve.h.

Referenced by VCS_SOLVE::vcs_report().

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

Definition at line 1976 of file vcs_solve.h.

Referenced by VCS_SOLVE::vcs_nondim_TP(), VCS_SOLVE::vcs_redim_TP(), and VCS_SOLVE::vcs_report().

 VCS_COUNTERS* m_VCount

Timing and iteration counters for the vcs object.

Definition at line 1979 of file vcs_solve.h.

 int m_debug_print_lvl

Debug printing lvl.

Levels correspond to the following guidlines

• 0 No printing at all
• 1 Serious warnings or fatal errors get one line
• 2 one line per eacdh 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

Levels of printing above 4 are only accessible when DEBUG_MODE is turned on

Definition at line 1995 of file vcs_solve.h.

 int m_timing_print_lvl

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 2002 of file vcs_solve.h.

 int m_VCS_UnitsFormat

Units for the chemical potential data.

Value chemical potential units pressure units
-1 kcal/mol Pa
0 MU/RT Pa
1 kJ/mol Pa
2 Kelvin Pa
3 J / kmol Pa

Definition at line 2014 of file vcs_solve.h.

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