cantera/Cantera/src/equil/vcs_VolPhase.cpp
2008-08-18 23:17:18 +00:00

1586 lines
46 KiB
C++

/**
* @file vcs_VolPhase.cpp
*/
/* $Id$ */
/*
* Copywrite (2005) Sandia Corporation. Under the terms of
* Contract DE-AC04-94AL85000 with Sandia Corporation, the
* U.S. Government retains certain rights in this software.
*/
#include "vcs_VolPhase.h"
#include "vcs_internal.h"
#include "vcs_SpeciesProperties.h"
#include "vcs_species_thermo.h"
#include "vcs_solve.h"
#include "ThermoPhase.h"
#include "mix_defs.h"
#include <string>
#include <cstdio>
#include <cstdlib>
namespace VCSnonideal {
/*
*
* vcs_VolPhase():
*
* Constructor for the VolPhase object.
*/
vcs_VolPhase::vcs_VolPhase(VCS_SOLVE * owningSolverObject) :
m_owningSolverObject(0),
VP_ID(-1),
Domain_ID(-1),
m_singleSpecies(true),
m_gasPhase(false),
m_eqnState(VCS_EOS_CONSTANT),
ChargeNeutralityElement(-1),
p_VCS_UnitsFormat(VCS_UNITS_MKS),
p_activityConvention(0),
m_numElemConstraints(0),
m_elemGlobalIndex(0),
m_numSpecies(0),
m_totalMolesInert(0.0),
m_isIdealSoln(false),
m_existence(VCS_PHASE_EXIST_NO),
m_MFStartIndex(0),
IndSpecies(0),
m_useCanteraCalls(false),
TP_ptr(0),
v_totalMoles(0.0),
m_totalVol(0.0),
m_vcsStateStatus(VCS_STATECALC_OLD),
m_phi(0.0),
m_UpToDate(false),
m_UpToDate_AC(false),
m_UpToDate_VolStar(false),
m_UpToDate_VolPM(false),
m_UpToDate_GStar(false),
m_UpToDate_G0(false),
Temp(273.15),
Pres(1.01325E5),
RefPres(1.01325E5)
{
m_owningSolverObject = owningSolverObject;
}
/***************************************************************************/
/*
*
* ~vcs_VolPhase():
*
* Destructor for the VolPhase object.
*/
vcs_VolPhase::~vcs_VolPhase() {
for (int k = 0; k < m_numSpecies; k++) {
vcs_SpeciesProperties *sp = ListSpeciesPtr[k];
delete sp;
sp = 0;
}
}
/************************************************************************************/
/*
*
* Copy Constructor():
*
* Objects that are owned by this object are deep copied here, except
* for the ThermoPhase object.
* The assignment operator does most of the work.
*/
vcs_VolPhase::vcs_VolPhase(const vcs_VolPhase& b) :
m_owningSolverObject(b.m_owningSolverObject),
VP_ID(b.VP_ID),
Domain_ID(b.Domain_ID),
m_singleSpecies(b.m_singleSpecies),
m_gasPhase(b.m_gasPhase),
m_eqnState(b.m_eqnState),
ChargeNeutralityElement(b.ChargeNeutralityElement),
p_VCS_UnitsFormat(b.p_VCS_UnitsFormat),
p_activityConvention(b.p_activityConvention),
m_numElemConstraints(b.m_numElemConstraints),
m_numSpecies(b.m_numSpecies),
m_totalMolesInert(b.m_totalMolesInert),
m_isIdealSoln(b.m_isIdealSoln),
m_existence(b.m_existence),
m_MFStartIndex(b.m_MFStartIndex),
m_useCanteraCalls(b.m_useCanteraCalls),
TP_ptr(b.TP_ptr),
v_totalMoles(b.v_totalMoles),
m_phiVarIndex(-1),
m_totalVol(b.m_totalVol),
m_vcsStateStatus(VCS_STATECALC_OLD),
m_phi(b.m_phi),
m_UpToDate(false),
m_UpToDate_AC(false),
m_UpToDate_VolStar(false),
m_UpToDate_VolPM(false),
m_UpToDate_GStar(false),
m_UpToDate_G0(false),
Temp(b.Temp),
Pres(b.Pres)
{
/*
* Call the Assignment operator to do the heavy
* lifting.
*/
*this = b;
}
/***************************************************************************/
/*
* Assignment operator()
*
* (note, this is used, so keep it current!)
*/
vcs_VolPhase& vcs_VolPhase::operator=(const vcs_VolPhase& b) {
int k;
if (&b != this) {
int old_num = m_numSpecies;
// Note: we comment this out for the assignment operator
// specifically, because it isn't true for the assignment
// operator but is true for a copy constructor
// m_owningSolverObject = b.m_owningSolverObject;
VP_ID = b.VP_ID;
Domain_ID = b.Domain_ID;
m_singleSpecies = b.m_singleSpecies;
m_gasPhase = b.m_gasPhase;
m_eqnState = b.m_eqnState;
m_numSpecies = b.m_numSpecies;
m_numElemConstraints = b.m_numElemConstraints;
ChargeNeutralityElement = b.ChargeNeutralityElement;
m_elementNames.resize(b.m_numElemConstraints);
for (int e = 0; e < b.m_numElemConstraints; e++) {
m_elementNames[e] = b.m_elementNames[e];
}
m_elementActive = b.m_elementActive;
m_elementType = b.m_elementType;
m_formulaMatrix.resize(m_numElemConstraints, m_numSpecies, 0.0);
for (int e = 0; e < m_numElemConstraints; e++) {
for (int k = 0; k < m_numSpecies; k++) {
m_formulaMatrix[e][k] = b.m_formulaMatrix[e][k];
}
}
m_speciesUnknownType = b.m_speciesUnknownType;
m_elemGlobalIndex = b.m_elemGlobalIndex;
m_numSpecies = b.m_numSpecies;
PhaseName = b.PhaseName;
m_totalMolesInert = b.m_totalMolesInert;
p_activityConvention= b.p_activityConvention;
m_isIdealSoln = b.m_isIdealSoln;
m_existence = b.m_existence;
m_MFStartIndex = b.m_MFStartIndex;
/*
* Do a shallow copy because we haven' figured this out.
*/
IndSpecies = b.IndSpecies;
//IndSpeciesContig = b.IndSpeciesContig;
for (k = 0; k < old_num; k++) {
if ( ListSpeciesPtr[k]) {
delete ListSpeciesPtr[k];
ListSpeciesPtr[k] = 0;
}
}
ListSpeciesPtr.resize(m_numSpecies, 0);
for (k = 0; k < m_numSpecies; k++) {
ListSpeciesPtr[k] =
new vcs_SpeciesProperties(*(b.ListSpeciesPtr[k]));
}
p_VCS_UnitsFormat = b.p_VCS_UnitsFormat;
m_useCanteraCalls = b.m_useCanteraCalls;
/*
* Do a shallow copy of the ThermoPhase object pointer.
* We don't duplicate the object.
* Um, there is no reason we couldn't do a
* duplicateMyselfAsThermoPhase() call here. This will
* have to be looked into.
*/
TP_ptr = b.TP_ptr;
v_totalMoles = b.v_totalMoles;
Xmol = b.Xmol;
m_phi = b.m_phi;
m_phiVarIndex = b.m_phiVarIndex;
SS0ChemicalPotential = b.SS0ChemicalPotential;
StarChemicalPotential = b.StarChemicalPotential;
StarMolarVol = b.StarMolarVol;
PartialMolarVol = b.PartialMolarVol;
ActCoeff = b.ActCoeff;
dLnActCoeffdMolNumber = b.dLnActCoeffdMolNumber;
m_UpToDate = false;
m_vcsStateStatus = b.m_vcsStateStatus;
m_UpToDate_AC = false;
m_UpToDate_VolStar = false;
m_UpToDate_VolPM = false;
m_UpToDate_GStar = false;
m_UpToDate_G0 = false;
Temp = b.Temp;
Pres = b.Pres;
setState_TP(Temp, Pres);
_updateMoleFractionDependencies();
}
return *this;
}
/***************************************************************************/
void vcs_VolPhase::resize(const int phaseNum, const int nspecies,
const int numElem, const char * const phaseName,
const double molesInert) {
#ifdef DEBUG_MODE
if (nspecies <= 0) {
plogf("nspecies Error\n");
std::exit(-1);
}
if (phaseNum < 0) {
plogf("phaseNum should be greater than 0\n");
std::exit(-1);
}
#endif
setTotalMolesInert(molesInert);
m_phi = 0.0;
m_phiVarIndex = -1;
if (phaseNum == VP_ID) {
if (strcmp(PhaseName.c_str(), phaseName)) {
plogf("Strings are different: %s %s :unknown situation\n",
PhaseName.c_str(), phaseName);
std::exit(-1);
}
} else {
VP_ID = phaseNum;
if (!phaseName) {
char itmp[40];
sprintf(itmp, "Phase_%d", VP_ID);
PhaseName = itmp;
} else {
PhaseName = phaseName;
}
}
if (nspecies > 1) {
m_singleSpecies = false;
} else {
m_singleSpecies = true;
}
if (m_numSpecies == nspecies && numElem == m_numElemConstraints) {
return;
}
m_numSpecies = nspecies;
if (nspecies > 1) {
m_singleSpecies = false;
}
IndSpecies.resize(nspecies, -1);
if ((int) ListSpeciesPtr.size() >= m_numSpecies) {
for (int i = 0; i < m_numSpecies; i++) {
if (ListSpeciesPtr[i]) {
delete ListSpeciesPtr[i];
ListSpeciesPtr[i] = 0;
}
}
}
ListSpeciesPtr.resize(nspecies, 0);
for (int i = 0; i < nspecies; i++) {
ListSpeciesPtr[i] = new vcs_SpeciesProperties(phaseNum, i, this);
}
Xmol.resize(nspecies, 0.0);
for (int i = 0; i < nspecies; i++) {
Xmol[i] = 1.0/nspecies;
}
SS0ChemicalPotential.resize(nspecies, -1.0);
StarChemicalPotential.resize(nspecies, -1.0);
StarMolarVol.resize(nspecies, -1.0);
PartialMolarVol.resize(nspecies, -1.0);
ActCoeff.resize(nspecies, 1.0);
dLnActCoeffdMolNumber.resize(nspecies, nspecies, 0.0);
m_speciesUnknownType.resize(nspecies, VCS_SPECIES_TYPE_MOLNUM);
m_UpToDate = false;
m_vcsStateStatus = VCS_STATECALC_OLD;
m_UpToDate_AC = false;
m_UpToDate_VolStar = false;
m_UpToDate_VolPM = false;
m_UpToDate_GStar = false;
m_UpToDate_G0 = false;
elemResize(numElem);
}
/***************************************************************************/
void vcs_VolPhase::elemResize(const int numElemConstraints) {
m_elementNames.resize(numElemConstraints);
m_elementActive.resize(numElemConstraints+1, 1);
m_elementType.resize(numElemConstraints, VCS_ELEM_TYPE_ABSPOS);
m_formulaMatrix.resize(numElemConstraints, m_numSpecies, 0.0);
m_elementNames.resize(numElemConstraints, "");
m_elemGlobalIndex.resize(numElemConstraints, -1);
m_numElemConstraints = numElemConstraints;
}
/***************************************************************************/
//! Evaluate activity coefficients
/*!
* We carry out a calculation whenever UpTODate_AC is false. Specifically
* whenever a phase goes zero, we do not carry out calculations on it.
*
* (private)
*/
void vcs_VolPhase::_updateActCoeff() const {
if (m_isIdealSoln) {
m_UpToDate_AC = true;
return;
}
if (m_useCanteraCalls) {
TP_ptr->getActivityCoefficients(VCS_DATA_PTR(ActCoeff));
}
m_UpToDate_AC = true;
}
/***************************************************************************/
/*
*
* Evaluate one activity coefficients.
*
* return one activity coefficient. Have to recalculate them all to get
* one.
*/
double vcs_VolPhase::AC_calc_one(int kspec) const {
if (! m_UpToDate_AC) {
_updateActCoeff();
}
return(ActCoeff[kspec]);
}
/***************************************************************************/
// Gibbs free energy calculation at a temperature for the reference state
// of each species
/*
*/
void vcs_VolPhase::_updateG0() const {
if (m_useCanteraCalls) {
TP_ptr->getGibbs_ref(VCS_DATA_PTR(SS0ChemicalPotential));
} else {
double R = vcsUtil_gasConstant(p_VCS_UnitsFormat);
for (int k = 0; k < m_numSpecies; k++) {
int kglob = IndSpecies[k];
vcs_SpeciesProperties *sProp = ListSpeciesPtr[k];
VCS_SPECIES_THERMO *sTherm = sProp->SpeciesThermo;
SS0ChemicalPotential[k] =
R * (sTherm->G0_R_calc(kglob, Temp));
}
}
m_UpToDate_G0 = true;
}
/***************************************************************************/
// Gibbs free energy calculation at a temperature for the reference state
// of a species, return a value for one species
/*
* @param kspec species index
* @param TKelvin temperature
*
* @return return value of the gibbs free energy
*/
double vcs_VolPhase::G0_calc_one(int kspec) const {
if (!m_UpToDate_G0) {
_updateG0();
}
return SS0ChemicalPotential[kspec];
}
/***************************************************************************/
// Gibbs free energy calculation for standard states
/*
* Calculate the Gibbs free energies for the standard states
* The results are held internally within the object.
*
* @param TKelvin Current temperature
* @param pres Current pressure (pascal)
*/
void vcs_VolPhase::_updateGStar() const {
if (m_useCanteraCalls) {
TP_ptr->getStandardChemPotentials(VCS_DATA_PTR(StarChemicalPotential));
} else {
double R = vcsUtil_gasConstant(p_VCS_UnitsFormat);
for (int k = 0; k < m_numSpecies; k++) {
int kglob = IndSpecies[k];
vcs_SpeciesProperties *sProp = ListSpeciesPtr[k];
VCS_SPECIES_THERMO *sTherm = sProp->SpeciesThermo;
StarChemicalPotential[k] =
R * (sTherm->GStar_R_calc(kglob, Temp, Pres));
}
}
m_UpToDate_GStar = true;
}
/***************************************************************************/
// Gibbs free energy calculation for standard state of one species
/*
* Calculate the Gibbs free energies for the standard state
* of the kth species.
* The results are held internally within the object.
* The kth species standard state G is returned
*
* @param kspec Species number (within the phase)
*
* @return Gstar[kspec] returns the gibbs free energy for the
* standard state of the kspec species.
*/
double vcs_VolPhase::GStar_calc_one(int kspec) const {
if (!m_UpToDate_GStar) {
_updateGStar();
}
return StarChemicalPotential[kspec];
}
/***************************************************************************/
// Set the mole fractions from a conventional mole fraction vector
/*
*
* @param xmol Value of the mole fractions for the species
* in the phase. These are contiguous.
*/
void vcs_VolPhase::setMoleFractions(const double * const xmol) {
double sum = -1.0;
for (int k = 0; k < m_numSpecies; k++) {
Xmol[k] = xmol[k];
sum+= xmol[k];
}
if (std::fabs(sum) > 1.0E-13) {
for (int k = 0; k < m_numSpecies; k++) {
Xmol[k] /= sum;
}
}
_updateMoleFractionDependencies();
m_UpToDate = false;
m_vcsStateStatus = VCS_STATECALC_TMP;
}
/***************************************************************************/
// Updates the mole fractions in subobjects
/*
* Whenever the mole fractions change, this routine
* should be called.
*/
void vcs_VolPhase::_updateMoleFractionDependencies() {
if (m_useCanteraCalls) {
if (TP_ptr) {
TP_ptr->setState_PX(Pres, &(Xmol[m_MFStartIndex]));
}
}
if (!m_isIdealSoln) {
m_UpToDate_AC = false;
m_UpToDate_VolPM = false;
}
}
/***************************************************************************/
// Return a const reference to the mole fraction vector in the phase
const std::vector<double> & vcs_VolPhase::moleFractions() const {
return Xmol;
}
/***************************************************************************/
// Set the moles and/or mole fractions within the phase
/*
*
*
*/
void vcs_VolPhase::setMoleFractionsState(double totalMoles,
const double * moleFractions,
const int vcsStateStatus) {
if (totalMoles != 0.0) {
if (vcsStateStatus != VCS_STATECALC_TMP) {
printf("vcs_VolPhase::setMolesFractionsState: inappropriate usage\n");
std::exit(-1);
}
m_UpToDate = false;
m_vcsStateStatus = VCS_STATECALC_TMP;
if (m_existence == -VCS_PHASE_EXIST_ZEROEDPHASE ) {
printf("vcs_VolPhase::setMolesFractionsState: inappropriate usage\n");
std::exit(-1);
}
m_existence = VCS_PHASE_EXIST_YES;
} else {
m_UpToDate = true;
m_vcsStateStatus = vcsStateStatus;
if (m_existence > VCS_PHASE_EXIST_NO ) {
m_existence = VCS_PHASE_EXIST_NO;
}
}
double sum = 0.0;
for (int k = 0; k < m_numSpecies; k++) {
Xmol[k] = moleFractions[k];
sum += moleFractions[k];
}
if (sum == 0.0) {
printf("vcs_VolPhase::setMolesFractionsState: inappropriate usage\n");
std::exit(-1);
}
if (sum != 1.0) {
for (int k = 0; k < m_numSpecies; k++) {
Xmol[k] /= sum;
}
}
_updateMoleFractionDependencies();
}
/***************************************************************************/
// Set the moles within the phase
/*
* This function takes as input the mole numbers in vcs format, and
* then updates this object with their values. This is essentially
* a gather routine.
*
*
* @param molesSpeciesVCS array of mole numbers. Note, the indecises
* for species in
* this array may not be contiguous. IndSpecies[] is needed
* to gather the species into the local contiguous vector
* format.
*/
void vcs_VolPhase::setMolesFromVCS(const int stateCalc,
const double * molesSpeciesVCS) {
int kglob;
double tmp;
v_totalMoles = m_totalMolesInert;
if (molesSpeciesVCS == 0) {
#ifdef DEBUG_MODE
if (m_owningSolverObject == 0) {
printf("vcs_VolPhase::setMolesFromVCS shouldn't be here\n");
std::exit(-1);
}
#endif
if (stateCalc == VCS_STATECALC_OLD) {
molesSpeciesVCS = VCS_DATA_PTR(m_owningSolverObject->m_molNumSpecies_old);
} else if (stateCalc == VCS_STATECALC_NEW) {
molesSpeciesVCS = VCS_DATA_PTR(m_owningSolverObject->m_molNumSpecies_new);
}
#ifdef DEBUG_MODE
else {
printf("vcs_VolPhase::setMolesFromVCS shouldn't be here\n");
std::exit(-1);
}
#endif
}
#ifdef DEBUG_MODE
else {
if (m_owningSolverObject) {
if (stateCalc == VCS_STATECALC_OLD) {
if (molesSpeciesVCS != VCS_DATA_PTR(m_owningSolverObject->m_molNumSpecies_old)) {
printf("vcs_VolPhase::setMolesFromVCS shouldn't be here\n");
std::exit(-1);
}
} else if (stateCalc == VCS_STATECALC_NEW) {
if (molesSpeciesVCS != VCS_DATA_PTR(m_owningSolverObject->m_molNumSpecies_new)) {
printf("vcs_VolPhase::setMolesFromVCS shouldn't be here\n");
std::exit(-1);
}
}
}
}
#endif
for (int k = 0; k < m_numSpecies; k++) {
if (m_speciesUnknownType[k] != VCS_SPECIES_TYPE_INTERFACIALVOLTAGE) {
kglob = IndSpecies[k];
v_totalMoles += MAX(0.0, molesSpeciesVCS[kglob]);
}
}
if (v_totalMoles > 0.0) {
for (int k = 0; k < m_numSpecies; k++) {
if (m_speciesUnknownType[k] != VCS_SPECIES_TYPE_INTERFACIALVOLTAGE) {
kglob = IndSpecies[k];
tmp = MAX(0.0, molesSpeciesVCS[kglob]);
Xmol[k] = tmp / v_totalMoles;
}
}
m_existence = VCS_PHASE_EXIST_YES;
} else {
// This is where we will start to store a better approximation
// for the mole fractions, when the phase doesn't exist.
// This is currently unimplemented.
//for (int k = 0; k < m_numSpecies; k++) {
// Xmol[k] = 1.0 / m_numSpecies;
//}
m_existence = VCS_PHASE_EXIST_NO;
}
/*
* Update the electric potential if it is a solution variable
* in the equation system
*/
if (m_phiVarIndex >= 0) {
kglob = IndSpecies[m_phiVarIndex];
if (m_numSpecies == 1) {
Xmol[m_phiVarIndex] = 1.0;
} else {
Xmol[m_phiVarIndex] = 0.0;
}
double phi = molesSpeciesVCS[kglob];
setElectricPotential(phi);
if (m_numSpecies == 1) {
m_existence = VCS_PHASE_EXIST_YES;
}
}
_updateMoleFractionDependencies();
if (m_totalMolesInert > 0.0) {
m_existence = VCS_PHASE_EXIST_ALWAYS;
}
/*
* Set flags indicating we are up to date with the VCS state vector.
*/
m_UpToDate = true;
m_vcsStateStatus = stateCalc;
}
/***************************************************************************/
// Set the moles within the phase
/*
* This function takes as input the mole numbers in vcs format, and
* then updates this object with their values. This is essentially
* a gather routine.
*
*
* @param molesSpeciesVCS array of mole numbers. Note,
* the indecises for species in
* this array may not be contiguous. IndSpecies[] is needed
* to gather the species into the local contiguous vector
* format.
*/
void vcs_VolPhase::setMolesFromVCSCheck(const int stateCalc,
const double * molesSpeciesVCS,
const double * const TPhMoles) {
setMolesFromVCS(stateCalc, molesSpeciesVCS);
/*
* Check for consistency with TPhMoles[]
*/
double Tcheck = TPhMoles[VP_ID];
if (Tcheck != v_totalMoles) {
if (vcs_doubleEqual(Tcheck, v_totalMoles)) {
Tcheck = v_totalMoles;
} else {
plogf("vcs_VolPhase::setMolesFromVCSCheck: "
"We have a consistency problem: %21.16g %21.16g\n",
Tcheck, v_totalMoles);
std::exit(-1);
}
}
}
/***************************************************************************/
// Update the moles within the phase, if necessary
/*
* This function takes as input the stateCalc value, which
* determines where within VCS_SOLVE to fetch the mole numbers.
* It then updates this object with their values. This is essentially
* a gather routine.
*
* @param stateCalc State calc value either VCS_STATECALC_OLD
* or VCS_STATECALC_NEW. With any other value
* nothing is done.
*
*/
void vcs_VolPhase::updateFromVCS_MoleNumbers(const int stateCalc) {
if (!m_UpToDate || (stateCalc != m_vcsStateStatus)) {
if (stateCalc == VCS_STATECALC_OLD || stateCalc == VCS_STATECALC_NEW) {
if (m_owningSolverObject) {
setMolesFromVCS(stateCalc);
}
}
}
}
/**************************************************************************/
// Fill in an activity coefficients vector within a VCS_SOLVE object
/*
* This routine will calculate the activity coefficients for the
* current phase, and fill in the corresponding entries in the
* VCS activity coefficients vector.
*
* @param AC vector of activity coefficients for all of the species
* in all of the phases in a VCS problem. Only the
* entries for the current phase are filled in.
*/
void vcs_VolPhase::sendToVCS_ActCoeff(const int stateCalc,
double * const AC) {
updateFromVCS_MoleNumbers(stateCalc);
if (!m_UpToDate_AC) {
_updateActCoeff();
}
int kglob;
for (int k = 0; k < m_numSpecies; k++) {
kglob = IndSpecies[k];
AC[kglob] = ActCoeff[k];
}
}
/***************************************************************************/
// Fill in the partial molar volume vector for VCS
/*
* This routine will calculate the partial molar volumes for the
* current phase (if needed), and fill in the corresponding entries in the
* VCS partial molar volumes vector.
*
* @param VolPM vector of partial molar volumes for all of the species
* in all of the phases in a VCS problem. Only the
* entries for the current phase are filled in.
*/
double vcs_VolPhase::sendToVCS_VolPM(double * const VolPM) const {
if (!m_UpToDate_VolPM) {
(void) _updateVolPM();
}
int kglob;
for (int k = 0; k < m_numSpecies; k++) {
kglob = IndSpecies[k];
VolPM[kglob] = PartialMolarVol[k];
}
return m_totalVol;
}
/***************************************************************************/
// Fill in the partial molar volume vector for VCS
/*
* This routine will calculate the partial molar volumes for the
* current phase (if needed), and fill in the corresponding entries in the
* VCS partial molar volumes vector.
*
* @param VolPM vector of partial molar volumes for all of the species
* in all of the phases in a VCS problem. Only the
* entries for the current phase are filled in.
*/
void vcs_VolPhase::sendToVCS_GStar(double * const gstar) const {
if (!m_UpToDate_GStar) {
_updateGStar();
}
int kglob;
for (int k = 0; k < m_numSpecies; k++) {
kglob = IndSpecies[k];
gstar[kglob] = StarChemicalPotential[k];
}
}
/***************************************************************************/
void vcs_VolPhase::setElectricPotential(const double phi) {
m_phi = phi;
if (m_useCanteraCalls) {
TP_ptr->setElectricPotential(m_phi);
}
// We have changed the state variable. Set uptodate flags to false
m_UpToDate_AC = false;
m_UpToDate_VolStar = false;
m_UpToDate_VolPM = false;
m_UpToDate_GStar = false;
}
/***************************************************************************/
double vcs_VolPhase::electricPotential() const {
return m_phi;
}
/***************************************************************************/
// Sets the temperature and pressure in this object and
// underlying objects
/*
* Sets the temperature and pressure in this object and
* underlying objects. The underlying objects refers to the
* Cantera's ThermoPhase object for this phase.
*
* @param temperature_Kelvin (Kelvin)
* @param pressure_PA Pressure (MKS units - Pascal)
*/
void vcs_VolPhase::setState_TP(const double temp, const double pres)
{
if (Temp == temp) {
if (Pres == pres) {
return;
}
}
if (m_useCanteraCalls) {
TP_ptr->setElectricPotential(m_phi);
TP_ptr->setState_TP(temp, pres);
}
Temp = temp;
Pres = pres;
m_UpToDate_AC = false;
m_UpToDate_VolStar = false;
m_UpToDate_VolPM = false;
m_UpToDate_GStar = false;
m_UpToDate_G0 = false;
}
/***************************************************************************/
// Sets the temperature in this object and
// underlying objects
/*
* Sets the temperature and pressure in this object and
* underlying objects. The underlying objects refers to the
* Cantera's ThermoPhase object for this phase.
*
* @param temperature_Kelvin (Kelvin)
*/
void vcs_VolPhase::setState_T(const double temp) {
setState_TP(temp, Pres);
}
/***************************************************************************/
// Molar volume calculation for standard states
/*
* Calculate the molar volume for the standard states
* The results are held internally within the object.
*
* @param TKelvin Current temperature
* @param pres Current pressure (pascal)
*
* Calculations are in m**3 / kmol
*/
void vcs_VolPhase::_updateVolStar() const {
if (m_useCanteraCalls) {
TP_ptr->getStandardVolumes(VCS_DATA_PTR(StarMolarVol));
} else {
for (int k = 0; k < m_numSpecies; k++) {
int kglob = IndSpecies[k];
vcs_SpeciesProperties *sProp = ListSpeciesPtr[k];
VCS_SPECIES_THERMO *sTherm = sProp->SpeciesThermo;
StarMolarVol[k] = (sTherm->VolStar_calc(kglob, Temp, Pres));
}
}
m_UpToDate_VolStar = true;
}
/***************************************************************************/
// Molar volume calculation for standard state of one species
/*
* Calculate the molar volume for the standard states
* The results are held internally within the object.
* Return the molar volume for one species
*
* @param kspec Species number (within the phase)
* @param TKelvin Current temperature
* @param pres Current pressure (pascal)
*
* @return molar volume of the kspec species's standard
* state
*/
double vcs_VolPhase::VolStar_calc_one(int kspec) const {
if (!m_UpToDate_VolStar) {
_updateVolStar();
}
return StarMolarVol[kspec];
}
/***************************************************************************/
// Calculate the partial molar volumes of all species and return the
// total volume
/*
* Calculates these quantitites internally and then stores them
*
* @return total volume (m**3)
*/
double vcs_VolPhase::_updateVolPM() const {
int k, kglob;
if (m_useCanteraCalls) {
TP_ptr->getPartialMolarVolumes(VCS_DATA_PTR(PartialMolarVol));
} else {
for (k = 0; k < m_numSpecies; k++) {
kglob = IndSpecies[k];
vcs_SpeciesProperties *sProp = ListSpeciesPtr[k];
VCS_SPECIES_THERMO *sTherm = sProp->SpeciesThermo;
StarMolarVol[k] = (sTherm->VolStar_calc(kglob, Temp, Pres));
}
for (k = 0; k < m_numSpecies; k++) {
PartialMolarVol[k] = StarMolarVol[k];
}
}
m_totalVol = 0.0;
for (k = 0; k < m_numSpecies; k++) {
m_totalVol += PartialMolarVol[k] * Xmol[k];
}
m_totalVol *= v_totalMoles;
if (m_totalMolesInert > 0.0) {
if (m_gasPhase) {
double volI = m_totalMolesInert * 8314.47215 * Temp / Pres;
m_totalVol += volI;
} else {
printf("unknown situation\n");
std::exit(-1);
}
}
m_UpToDate_VolPM = true;
return m_totalVol;
}
/***************************************************************************/
/*
* _updateLnActCoeffJac():
*
*/
void vcs_VolPhase::_updateLnActCoeffJac() {
int k, j;
double deltaMoles_j = 0.0;
/*
* Evaluate the current base activity coefficients if necessary
*/
if (!m_UpToDate_AC) {
_updateActCoeff();
}
// Make copies of ActCoeff and Xmol for use in taking differences
std::vector<double> ActCoeff_Base(ActCoeff);
std::vector<double> Xmol_Base(Xmol);
double TMoles_base = v_totalMoles;
/*
* Loop over the columns species to be deltad
*/
for (j = 0; j < m_numSpecies; j++) {
/*
* Calculate a value for the delta moles of species j
* -> NOte Xmol[] and Tmoles are always positive or zero
* quantities.
*/
double moles_j_base = v_totalMoles * Xmol_Base[j];
deltaMoles_j = 1.0E-7 * moles_j_base + 1.0E-20 * v_totalMoles + 1.0E-150;
/*
* Now, update the total moles in the phase and all of the
* mole fractions based on this.
*/
v_totalMoles = TMoles_base + deltaMoles_j;
for (k = 0; k < m_numSpecies; k++) {
Xmol[k] = Xmol_Base[k] * TMoles_base / v_totalMoles;
}
Xmol[j] = (moles_j_base + deltaMoles_j) / v_totalMoles;
/*
* Go get new values for the activity coefficients.
* -> Note this calls setState_PX();
*/
_updateMoleFractionDependencies();
_updateActCoeff();
/*
* Calculate the column of the matrix
*/
double * const lnActCoeffCol = dLnActCoeffdMolNumber[j];
for (k = 0; k < m_numSpecies; k++) {
lnActCoeffCol[k] = (ActCoeff[k] - ActCoeff_Base[k]) /
((ActCoeff[k] + ActCoeff_Base[k]) * 0.5 * deltaMoles_j);
}
/*
* Revert to the base case Xmol, v_totalMoles
*/
v_totalMoles = TMoles_base;
vcs_vdcopy(Xmol, Xmol_Base, m_numSpecies);
}
/*
* Go get base values for the activity coefficients.
* -> Note this calls setState_TPX() again;
* -> Just wanted to make sure that cantera is in sync
* with VolPhase after this call.
*/
setMoleFractions(VCS_DATA_PTR(Xmol_Base));
_updateMoleFractionDependencies();
_updateActCoeff();
}
/***************************************************************************/
// Downloads the ln ActCoeff jacobian into the VCS version of the
// ln ActCoeff jacobian.
/*
*
* This is essentially a scatter operation.
*
* The Jacobians are actually d( lnActCoeff) / d (MolNumber);
* dLnActCoeffdMolNumber[j][k]
*
* j = id of the species mole number
* k = id of the species activity coefficient
*/
void
vcs_VolPhase::sendToVCS_LnActCoeffJac(double * const * const LnACJac_VCS) {
/*
* update the Ln Act Coeff jacobian entries with respect to the
* mole number of species in the phase -> we always assume that
* they are out of date.
*/
_updateLnActCoeffJac();
/*
* Now copy over the values
*/
int j, k, jglob, kglob;
for (j = 0; j < m_numSpecies; j++) {
jglob = IndSpecies[j];
double * const lnACJacVCS_col = LnACJac_VCS[jglob];
const double * const lnACJac_col = dLnActCoeffdMolNumber[j];
for (k = 0; k < m_numSpecies; k++) {
kglob = IndSpecies[k];
lnACJacVCS_col[kglob] = lnACJac_col[k];
}
}
}
/***************************************************************************/
// Set the pointer for Cantera's ThermoPhase parameter
/*
* When we first initialize the ThermoPhase object, we read the
* state of the ThermoPhase into vcs_VolPhase object.
*
* @param tp_ptr Pointer to the ThermoPhase object corresponding
* to this phase.
*/
void vcs_VolPhase::setPtrThermoPhase(Cantera::ThermoPhase *tp_ptr) {
TP_ptr = tp_ptr;
if (TP_ptr) {
m_useCanteraCalls = true;
Temp = TP_ptr->temperature();
Pres = TP_ptr->pressure();
setState_TP(Temp, Pres);
p_VCS_UnitsFormat = VCS_UNITS_MKS;
m_phi = TP_ptr->electricPotential();
int nsp = TP_ptr->nSpecies();
int nelem = TP_ptr->nElements();
if (nsp != m_numSpecies) {
if (m_numSpecies != 0) {
plogf("Warning Nsp != NVolSpeces: %d %d \n", nsp, m_numSpecies);
}
resize(VP_ID, nsp, nelem, PhaseName.c_str());
}
TP_ptr->getMoleFractions(VCS_DATA_PTR(Xmol));
_updateMoleFractionDependencies();
/*
* figure out ideal solution tag
*/
if (nsp == 1) {
m_isIdealSoln = true;
} else {
int eos = TP_ptr->eosType();
switch (eos) {
case Cantera::cIdealGas:
case Cantera::cIncompressible:
case Cantera::cSurf:
case Cantera::cMetal:
case Cantera::cStoichSubstance:
case Cantera::cSemiconductor:
case Cantera::cLatticeSolid:
case Cantera::cLattice:
case Cantera::cEdge:
case Cantera::cIdealSolidSolnPhase:
m_isIdealSoln = true;
break;
default:
m_isIdealSoln = false;
};
}
} else {
m_useCanteraCalls = false;
}
}
/***************************************************************************/
// Return a const ThermoPhase pointer corresponding to this phase
/*
* @return pointer to the ThermoPhase.
*/
const Cantera::ThermoPhase *vcs_VolPhase::ptrThermoPhase() const {
return TP_ptr;
}
/***************************************************************************/
double vcs_VolPhase::TotalMoles() const {
return v_totalMoles;
}
/***************************************************************************/
double vcs_VolPhase::molefraction(int k) const {
return Xmol[k];
}
/***************************************************************************/
// Sets the total moles in the phase
/*
* We don't have to flag the internal state as changing here
* because we have just changed the total moles.
*
* @param totalMols Total moles in the phase (kmol)
*/
void vcs_VolPhase::setTotalMoles(const double totalMols) {
v_totalMoles = totalMols;
if (m_totalMolesInert > 0.0) {
m_existence = VCS_PHASE_EXIST_ALWAYS;
#ifdef DEBUG_MODE
if (totalMols < m_totalMolesInert) {
printf(" vcs_VolPhase::setTotalMoles:: ERROR totalMoles "
"less than inert moles: %g %g\n",
totalMols, m_totalMolesInert);
std::exit(-1);
}
#endif
} else {
if (totalMols > 0.0) {
m_existence = VCS_PHASE_EXIST_YES;
} else {
m_existence = VCS_PHASE_EXIST_NO;
}
}
}
/***************************************************************************/
// Sets the mole flag within the object to out of date
/*
* This will trigger the object to go get the current mole numbers
* when it needs it.
*/
void vcs_VolPhase::setMolesOutOfDate(int stateCalc) {
m_UpToDate = false;
if (stateCalc != -1) {
m_vcsStateStatus = stateCalc;
}
}
/***************************************************************************/
// Sets the mole flag within the object to be current
/*
*
*/
void vcs_VolPhase::setMolesCurrent(int stateCalc) {
m_UpToDate = true;
m_vcsStateStatus = stateCalc;
}
/***************************************************************************/
// Return a string representing the equation of state
/*
* The string is no more than 16 characters.
* @param EOSType : integer value of the equation of state
*
* @return returns a string representing the EOS
*/
std::string string16_EOSType(int EOSType) {
char st[32];
st[16] = '\0';
switch (EOSType) {
case VCS_EOS_CONSTANT:
sprintf(st,"Constant ");
break;
case VCS_EOS_IDEAL_GAS:
sprintf(st,"Ideal Gas ");
break;
case VCS_EOS_STOICH_SUB:
sprintf(st,"Stoich Sub ");
break;
case VCS_EOS_IDEAL_SOLN:
sprintf(st,"Ideal Soln ");
break;
case VCS_EOS_DEBEYE_HUCKEL:
sprintf(st,"Debeye Huckel ");
break;
case VCS_EOS_REDLICK_KWONG:
sprintf(st,"Redlick_Kwong ");
break;
case VCS_EOS_REGULAR_SOLN:
sprintf(st,"Regular Soln ");
break;
default:
sprintf(st,"UnkType: %-7d", EOSType);
break;
}
st[16] = '\0';
std::string sss=st;
return sss;
}
/***************************************************************************/
// Returns whether the phase is an ideal solution phase
bool vcs_VolPhase::isIdealSoln() const {
return m_isIdealSoln;
}
/***************************************************************************/
// Returns whether the phase uses Cantera calls
bool vcs_VolPhase::usingCanteraCalls() const {
return m_useCanteraCalls;
}
/***************************************************************************/
int vcs_VolPhase::phiVarIndex() const {
return m_phiVarIndex;
}
/***************************************************************************/
void vcs_VolPhase::setPhiVarIndex(int phiVarIndex) {
m_phiVarIndex = phiVarIndex;
}
/***************************************************************************/
// Retrieve the kth Species structure for the species belonging to this phase
/*
* The index into this vector is the species index within the phase.
*
* @param kindex kth species index.
*/
vcs_SpeciesProperties * vcs_VolPhase::speciesProperty(const int kindex) {
return ListSpeciesPtr[kindex];
}
/***************************************************************************/
// Boolean indicating whether the phase exists or not
int vcs_VolPhase::exists() const {
return m_existence;
}
/**********************************************************************/
// Set the existence flag in the object
void vcs_VolPhase::setExistence(const int existence) {
if (existence == VCS_PHASE_EXIST_NO || existence == VCS_PHASE_EXIST_ZEROEDPHASE) {
if (v_totalMoles != 0.0) {
#ifdef DEBUG_MODE
plogf("vcs_VolPhase::setExistence setting false existence for phase with moles");
plogendl();
exit(-1);
#endif
v_totalMoles = 0.0;
}
}
#ifdef DEBUG_MODE
else {
if (m_totalMolesInert == 0.0) {
if (v_totalMoles == 0.0) {
plogf("vcs_VolPhase::setExistence setting true existence for phase with no moles");
plogendl();
exit(-1);
}
}
}
#endif
m_existence = existence;
}
/**********************************************************************/
// Return the Global VCS index of the kth species in the phase
/*
* @param spIndex local species index (0 to the number of species
* in the phase)
*
* @return Returns the VCS_SOLVE species index of the that species
* This changes as rearrangements are carried out.
*/
int vcs_VolPhase::spGlobalIndexVCS(const int spIndex) const {
return IndSpecies[spIndex];
}
/**********************************************************************/
//! set the Global VCS index of the kth species in the phase
/*!
* @param spIndex local species index (0 to the number of species
* in the phase)
*
* @return Returns the VCS_SOLVE species index of the that species
* This changes as rearrangements are carried out.
*/
void vcs_VolPhase::setSpGlobalIndexVCS(const int spIndex,
const int spGlobalIndex) {
IndSpecies[spIndex] = spGlobalIndex;
}
/**********************************************************************/
// Sets the total moles of inert in the phase
/*
* @param tMolesInert Value of the total kmols of inert species in the
* phase.
*/
void vcs_VolPhase::setTotalMolesInert(const double tMolesInert) {
if (m_totalMolesInert != tMolesInert) {
m_UpToDate = false;
m_UpToDate_AC = false;
m_UpToDate_VolStar = false;
m_UpToDate_VolPM = false;
m_UpToDate_GStar = false;
m_UpToDate_G0 = false;
v_totalMoles += (tMolesInert - m_totalMolesInert);
m_totalMolesInert = tMolesInert;
}
if (m_totalMolesInert > 0.0) {
m_existence = VCS_PHASE_EXIST_ALWAYS;
} else {
if (v_totalMoles > 0.0) {
m_existence = VCS_PHASE_EXIST_YES;
} else {
m_existence = VCS_PHASE_EXIST_NO;
}
}
}
/**********************************************************************/
// returns the value of the total kmol of inert in the phase
double vcs_VolPhase::totalMolesInert() const {
return m_totalMolesInert;
}
/**********************************************************************/
//! Returns the global index of the local element index for the phase
int vcs_VolPhase::elemGlobalIndex(const int e) const {
DebugAssertThrowVCS(e >= 0, " vcs_VolPhase::elemGlobalIndex") ;
DebugAssertThrowVCS(e < m_numElemConstraints, " vcs_VolPhase::elemGlobalIndex") ;
return m_elemGlobalIndex[e];
}
//! Returns the global index of the local element index for the phase
void vcs_VolPhase::setElemGlobalIndex(const int eLocal, const int eGlobal) {
DebugAssertThrowVCS(eLocal >= 0, "vcs_VolPhase::setElemGlobalIndex");
DebugAssertThrowVCS(eLocal < m_numElemConstraints,
"vcs_VolPhase::setElemGlobalIndex");
m_elemGlobalIndex[eLocal] = eGlobal;
}
int vcs_VolPhase::nElemConstraints() const {
return m_numElemConstraints;
}
std::string vcs_VolPhase::elementName(const int e) const {
return m_elementNames[e];
}
/*!
* This function decides whether a phase has charged species
* or not.
*/
static bool hasChargedSpecies(const Cantera::ThermoPhase * const tPhase) {
int nSpPhase = tPhase->nSpecies();
for (int k = 0; k < nSpPhase; k++) {
if (tPhase->charge(k) != 0.0) {
return true;
}
}
return false;
}
/**********************************************************************
*
* chargeNeutralityElement():
*
* This utility routine decides whether a Cantera ThermoPhase needs
* a constraint equation representing the charge neutrality of the
* phase. It does this by searching for charged species. If it
* finds one, and if the phase needs one, then it returns true.
*/
static bool chargeNeutralityElement(const Cantera::ThermoPhase * const tPhase) {
int hasCharge = hasChargedSpecies(tPhase);
if (tPhase->chargeNeutralityNecessary()) {
if (hasCharge) {
return true;
}
}
return false;
}
int vcs_VolPhase::transferElementsFM(const Cantera::ThermoPhase * const tPhase) {
int e, k, eT;
std::string ename;
int eFound = -2;
/*
*
*/
int nebase = tPhase->nElements();
int ne = nebase;
int ns = tPhase->nSpecies();
/*
* Decide whether we need an extra element constraint for charge
* neutrality of the phase
*/
bool cne = chargeNeutralityElement(tPhase);
if (cne) {
ChargeNeutralityElement = ne;
ne++;
}
/*
* Assign and malloc structures
*/
elemResize(ne);
if (ChargeNeutralityElement >= 0) {
m_elementType[ChargeNeutralityElement] = VCS_ELEM_TYPE_CHARGENEUTRALITY;
}
if (hasChargedSpecies(tPhase)) {
if (cne) {
/*
* We need a charge neutrality constraint.
* We also have an Electron Element. These are
* duplicates of each other. To avoid trouble with
* possible range error conflicts, sometimes we eliminate
* the Electron condition. Flag that condition for elimination
* by toggling the ElActive variable. If we find we need it
* later, we will retoggle ElActive to true.
*/
for (eT = 0; eT < nebase; eT++) {
ename = tPhase->elementName(eT);
if (ename == "E") {
eFound = eT;
m_elementActive[eT] = 0;
m_elementType[eT] = VCS_ELEM_TYPE_ELECTRONCHARGE;
}
}
} else {
for (eT = 0; eT < nebase; eT++) {
ename = tPhase->elementName(eT);
if (ename == "E") {
eFound = eT;
m_elementType[eT] = VCS_ELEM_TYPE_ELECTRONCHARGE;
}
}
}
if (eFound == -2) {
eFound = ne;
m_elementType[ne] = VCS_ELEM_TYPE_ELECTRONCHARGE;
m_elementActive[ne] = 0;
std::string ename = "E";
m_elementNames[ne] = ename;
ne++;
elemResize(ne);
}
}
m_formulaMatrix.resize(ne, ns, 0.0);
m_speciesUnknownType.resize(ns, VCS_SPECIES_TYPE_MOLNUM);
elemResize(ne);
//ElGlobalIndex.resize(ne, -1);
e = 0;
for (eT = 0; eT < nebase; eT++) {
ename = tPhase->elementName(eT);
m_elementNames[e] = ename;
e++;
}
if (cne) {
std::string pname = tPhase->id();
if (pname == "") {
char sss[50];
sprintf(sss, "phase%d", VP_ID);
pname = sss;
}
ename = "cn_" + pname;
e = ChargeNeutralityElement;
m_elementNames[e] = ename;
}
double * const * const fm = m_formulaMatrix.baseDataAddr();
for (k = 0; k < ns; k++) {
e = 0;
for (eT = 0; eT < nebase; eT++) {
fm[e][k] = tPhase->nAtoms(k, eT);
e++;
}
if (eFound >= 0) {
fm[eFound][k] = - tPhase->charge(k);
}
}
if (cne) {
for (k = 0; k < ns; k++) {
fm[ChargeNeutralityElement][k] = tPhase->charge(k);
}
}
/*
* Here, we figure out what is the species types are
* The logic isn't set in stone, and is just for a particular type
* of problem that I'm solving first.
*/
if (ns == 1) {
if (tPhase->charge(0) != 0.0) {
m_speciesUnknownType[0] = VCS_SPECIES_TYPE_INTERFACIALVOLTAGE;
setPhiVarIndex(0);
}
}
return ne;
}
// Type of the element constraint with index \c e.
/*
* @param e Element index.
*/
int vcs_VolPhase::elementType(const int e) const {
return m_elementType[e];
}
// Set the element Type of the element constraint with index \c e.
/*
* @param e Element index
* @param eType type of the element.
*/
void vcs_VolPhase::setElementType(const int e, const int eType) {
m_elementType[e] = eType;
}
double const * const * const vcs_VolPhase::getFormulaMatrix() const {
double const * const * const fm = m_formulaMatrix.constBaseDataAddr();
return fm;
}
int vcs_VolPhase::speciesUnknownType(const int k) const {
return m_speciesUnknownType[k];
}
int vcs_VolPhase::elementActive(const int e) const {
return m_elementActive[e];
}
//! Return the number of species in the phase
int vcs_VolPhase::nSpecies() const {
return m_numSpecies;
}
}