vcs_MultiPhaseEquil.cpp

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/**
 *  @file vcs_MultiPhaseEquil.cpp
 *    Driver routine for the VCSnonideal equilibrium solver package
 */
 
// This file is part of Cantera. See License.txt in the top-level directory or
// at https://cantera.org/license.txt for license and copyright information.
 
#include "cantera/equil/vcs_MultiPhaseEquil.h"
#include "cantera/equil/vcs_VolPhase.h"
#include "cantera/equil/vcs_species_thermo.h"
#include "cantera/base/clockWC.h"
#include "cantera/base/stringUtils.h"
#include "cantera/thermo/speciesThermoTypes.h"
#include "cantera/thermo/IdealSolidSolnPhase.h"
#include "cantera/thermo/IdealMolalSoln.h"
 
#include <cstdio>
 
namespace Cantera
{
vcs_MultiPhaseEquil::vcs_MultiPhaseEquil(MultiPhase* mix, int printLvl) :
    m_mix(mix),
    m_printLvl(printLvl),
    m_vsolve(mix, printLvl)
{
}
 
int vcs_MultiPhaseEquil::equilibrate_TV(int XY, double xtarget, int estimateEquil,
                                        int printLvl, double err,
                                        int maxsteps, int loglevel)
{
    double Vtarget = m_mix->volume();
    if ((XY != TV) && (XY != HV) && (XY != UV) && (XY != SV)) {
        throw CanteraError("vcs_MultiPhaseEquil::equilibrate_TV",
                           "Wrong XY flag: {}", XY);
    }
    int maxiter = 100;
    int iSuccess = 0;
    if (XY == TV) {
        m_mix->setTemperature(xtarget);
    }
    int strt = estimateEquil;
    double P1 = 0.0;
    double V1 = 0.0;
    double V2 = 0.0;
    double P2 = 0.0;
    double Tlow = 0.5 * m_mix->minTemp();
    double Thigh = 2.0 * m_mix->maxTemp();
    int printLvlSub = std::max(0, printLvl - 1);
    for (int n = 0; n < maxiter; n++) {
        double Pnow = m_mix->pressure();
 
        switch (XY) {
        case TV:
            iSuccess = equilibrate_TP(strt, printLvlSub, err, maxsteps, loglevel);
            break;
        case HV:
            iSuccess = equilibrate_HP(xtarget, HP, Tlow, Thigh, strt,
                                      printLvlSub, err, maxsteps, loglevel);
            break;
        case UV:
            iSuccess = equilibrate_HP(xtarget, UP, Tlow, Thigh, strt,
                                      printLvlSub, err, maxsteps, loglevel);
            break;
        case SV:
            iSuccess = equilibrate_SP(xtarget, Tlow, Thigh, strt,
                                      printLvlSub, err, maxsteps, loglevel);
            break;
        default:
            break;
        }
        strt = false;
        double Vnow = m_mix->volume();
        if (n == 0) {
            V2 = Vnow;
            P2 = Pnow;
        } else if (n == 1) {
            V1 = Vnow;
            P1 = Pnow;
        } else {
            P2 = P1;
            V2 = V1;
            P1 = Pnow;
            V1 = Vnow;
        }
 
        double Verr = fabs((Vtarget - Vnow)/Vtarget);
        if (Verr < err) {
            return iSuccess;
        }
        double Pnew;
        // find dV/dP
        if (n > 1) {
            double dVdP = (V2 - V1) / (P2 - P1);
            if (dVdP == 0.0) {
                throw CanteraError("vcs_MultiPhase::equilibrate_TV",
                                   "dVdP == 0.0");
            } else {
                Pnew = Pnow + (Vtarget - Vnow) / dVdP;
                if (Pnew < 0.2 * Pnow) {
                    Pnew = 0.2 * Pnow;
                }
                if (Pnew > 3.0 * Pnow) {
                    Pnew = 3.0 * Pnow;
                }
            }
        } else {
            m_mix->setPressure(Pnow*1.01);
            double dVdP = (m_mix->volume() - Vnow)/(0.01*Pnow);
            Pnew = Pnow + 0.5*(Vtarget - Vnow)/dVdP;
            if (Pnew < 0.5* Pnow) {
                Pnew = 0.5 * Pnow;
            }
            if (Pnew > 1.7 * Pnow) {
                Pnew = 1.7 * Pnow;
            }
        }
        m_mix->setPressure(Pnew);
    }
    throw CanteraError("vcs_MultiPhase::equilibrate_TV",
                       "No convergence for V");
}
 
int vcs_MultiPhaseEquil::equilibrate_HP(double Htarget, int XY, double Tlow,
    double Thigh, int estimateEquil, int printLvl, double err, int maxsteps,
    int loglevel)
{
    int maxiter = 100;
    int iSuccess;
    if (XY != HP && XY != UP) {
        throw CanteraError("vcs_MultiPhaseEquil::equilibrate_HP",
                           "Wrong XP", XY);
    }
    int strt = estimateEquil;
 
    // Lower bound on T. This will change as we progress in the calculation
    if (Tlow <= 0.0) {
        Tlow = 0.5 * m_mix->minTemp();
    }
    // Upper bound on T. This will change as we progress in the calculation
    if (Thigh <= 0.0 || Thigh > 1.0E6) {
        Thigh = 2.0 * m_mix->maxTemp();
    }
 
    double cpb = 1.0;
    double Hlow = Undef;
    double Hhigh = Undef;
    double Tnow = m_mix->temperature();
    int printLvlSub = std::max(printLvl - 1, 0);
 
    for (int n = 0; n < maxiter; n++) {
        // start with a loose error tolerance, but tighten it as we get
        // close to the final temperature
        try {
            Tnow = m_mix->temperature();
            iSuccess = equilibrate_TP(strt, printLvlSub, err, maxsteps, loglevel);
            strt = 0;
            double Hnow = (XY == UP) ? m_mix->IntEnergy() : m_mix->enthalpy();
            double pmoles[10];
            pmoles[0] = m_mix->phaseMoles(0);
            double Tmoles = pmoles[0];
            double HperMole = Hnow/Tmoles;
            if (printLvl > 0) {
                plogf("T = %g, Hnow = %g ,Tmoles = %g,  HperMole = %g\n",
                      Tnow, Hnow, Tmoles, HperMole);
            }
 
            // the equilibrium enthalpy monotonically increases with T;
            // if the current value is below the target, then we know the
            // current temperature is too low. Set the lower bounds.
            if (Hnow < Htarget) {
                if (Tnow > Tlow) {
                    Tlow = Tnow;
                    Hlow = Hnow;
                }
            } else {
                // the current enthalpy is greater than the target; therefore
                // the current temperature is too high. Set the high bounds.
                if (Tnow < Thigh) {
                    Thigh = Tnow;
                    Hhigh = Hnow;
                }
            }
            double dT;
            if (Hlow != Undef && Hhigh != Undef) {
                cpb = (Hhigh - Hlow)/(Thigh - Tlow);
                dT = (Htarget - Hnow)/cpb;
                double dTa = fabs(dT);
                double dTmax = 0.5*fabs(Thigh - Tlow);
                if (dTa > dTmax) {
                    dT *= dTmax/dTa;
                }
            } else {
                double Tnew = sqrt(Tlow*Thigh);
                dT = clip(Tnew - Tnow, -200.0, 200.0);
            }
            double acpb = std::max(fabs(cpb), 1.0E-6);
            double denom = std::max(fabs(Htarget), acpb);
            double Herr = Htarget - Hnow;
            double HConvErr = fabs((Herr)/denom);
            if (printLvl > 0) {
                plogf("   equilibrate_HP: It = %d, Tcurr  = %g Hcurr = %g, Htarget = %g\n",
                      n, Tnow, Hnow, Htarget);
                plogf("                   H rel error = %g, cp = %g, HConvErr = %g\n",
                      Herr, cpb, HConvErr);
            }
 
            if (HConvErr < err) { // || dTa < 1.0e-4) {
                if (printLvl > 0) {
                    plogf("   equilibrate_HP: CONVERGENCE: Hfinal  = %g Tfinal = %g, Its = %d \n",
                          Hnow, Tnow, n);
                    plogf("                   H rel error = %g, cp = %g, HConvErr = %g\n",
                          Herr, cpb, HConvErr);
                }
                return iSuccess;
            }
            double Tnew = Tnow + dT;
            if (Tnew < 0.0) {
                Tnew = 0.5*Tnow;
            }
            m_mix->setTemperature(Tnew);
        } catch (const CanteraError&) {
            if (!estimateEquil) {
                strt = -1;
            } else {
                double Tnew = 0.5*(Tnow + Thigh);
                if (fabs(Tnew - Tnow) < 1.0) {
                    Tnew = Tnow + 1.0;
                }
                m_mix->setTemperature(Tnew);
            }
        }
    }
    throw CanteraError("vcs_MultiPhaseEquil::equilibrate_HP",
                       "No convergence for T");
}
 
int vcs_MultiPhaseEquil::equilibrate_SP(double Starget, double Tlow, double Thigh,
    int estimateEquil, int printLvl, double err, int maxsteps, int loglevel)
{
    int maxiter = 100;
    int strt = estimateEquil;
 
    // Lower bound on T. This will change as we progress in the calculation
    if (Tlow <= 0.0) {
        Tlow = 0.5 * m_mix->minTemp();
    }
    // Upper bound on T. This will change as we progress in the calculation
    if (Thigh <= 0.0 || Thigh > 1.0E6) {
        Thigh = 2.0 * m_mix->maxTemp();
    }
 
    double cpb = 1.0, dT;
    double Slow = Undef;
    double Shigh = Undef;
    double Tnow = m_mix->temperature();
    Tlow = std::min(Tnow, Tlow);
    Thigh = std::max(Tnow, Thigh);
    int printLvlSub = std::max(printLvl - 1, 0);
 
    for (int n = 0; n < maxiter; n++) {
        // start with a loose error tolerance, but tighten it as we get
        // close to the final temperature
        try {
            Tnow = m_mix->temperature();
            int iSuccess = equilibrate_TP(strt, printLvlSub, err, maxsteps, loglevel);
            strt = 0;
            double Snow = m_mix->entropy();
            double pmoles[10];
            pmoles[0] = m_mix->phaseMoles(0);
            double Tmoles = pmoles[0];
            double SperMole = Snow/Tmoles;
            if (printLvl > 0) {
                plogf("T = %g, Snow = %g ,Tmoles = %g,  SperMole = %g\n",
                      Tnow, Snow, Tmoles, SperMole);
            }
 
            // the equilibrium entropy monotonically increases with T;
            // if the current value is below the target, then we know the
            // current temperature is too low. Set the lower bounds to the
            // current condition.
            if (Snow < Starget) {
                if (Tnow > Tlow) {
                    Tlow = Tnow;
                    Slow = Snow;
                } else {
                    if (Slow > Starget && Snow < Slow) {
                        Thigh = Tlow;
                        Shigh = Slow;
                        Tlow = Tnow;
                        Slow = Snow;
                    }
                }
            } else {
                // the current enthalpy is greater than the target; therefore
                // the current temperature is too high. Set the high bounds.
                if (Tnow < Thigh) {
                    Thigh = Tnow;
                    Shigh = Snow;
                }
            }
            if (Slow != Undef && Shigh != Undef) {
                cpb = (Shigh - Slow)/(Thigh - Tlow);
                dT = (Starget - Snow)/cpb;
                double Tnew = Tnow + dT;
                double dTa = fabs(dT);
                double dTmax = 0.5*fabs(Thigh - Tlow);
                if (Tnew > Thigh || Tnew < Tlow) {
                    dTmax = 1.5*fabs(Thigh - Tlow);
                }
                dTmax = std::min(dTmax, 300.);
                if (dTa > dTmax) {
                    dT *= dTmax/dTa;
                }
            } else {
                double Tnew = sqrt(Tlow*Thigh);
                dT = Tnew - Tnow;
            }
 
            double acpb = std::max(fabs(cpb), 1.0E-6);
            double denom = std::max(fabs(Starget), acpb);
            double Serr = Starget - Snow;
            double SConvErr = fabs((Serr)/denom);
            if (printLvl > 0) {
                plogf("   equilibrate_SP: It = %d, Tcurr  = %g Scurr = %g, Starget = %g\n",
                      n, Tnow, Snow, Starget);
                plogf("                   S rel error = %g, cp = %g, SConvErr = %g\n",
                      Serr, cpb, SConvErr);
            }
 
            if (SConvErr < err) { // || dTa < 1.0e-4) {
                if (printLvl > 0) {
                    plogf("   equilibrate_SP: CONVERGENCE: Sfinal  = %g Tfinal = %g, Its = %d \n",
                          Snow, Tnow, n);
                    plogf("                   S rel error = %g, cp = %g, HConvErr = %g\n",
                          Serr, cpb, SConvErr);
                }
                return iSuccess;
            }
            double Tnew = Tnow + dT;
            if (Tnew < 0.0) {
                Tnew = 0.5*Tnow;
            }
            m_mix->setTemperature(Tnew);
        } catch (const CanteraError&) {
            if (!estimateEquil) {
                strt = -1;
            } else {
                double Tnew = 0.5*(Tnow + Thigh);
                if (fabs(Tnew - Tnow) < 1.0) {
                    Tnew = Tnow + 1.0;
                }
                m_mix->setTemperature(Tnew);
            }
        }
    }
    throw CanteraError("vcs_MultiPhaseEquil::equilibrate_SP",
                       "No convergence for T");
}
 
int vcs_MultiPhaseEquil::equilibrate(int XY, int estimateEquil, int printLvl,
                                     double err, int maxsteps, int loglevel)
{
    double xtarget;
    if (XY == TP) {
        return equilibrate_TP(estimateEquil, printLvl, err, maxsteps, loglevel);
    } else if (XY == HP || XY == UP) {
        if (XY == HP) {
            xtarget = m_mix->enthalpy();
        } else {
            xtarget = m_mix->IntEnergy();
        }
        double Tlow = 0.5 * m_mix->minTemp();
        double Thigh = 2.0 * m_mix->maxTemp();
        return equilibrate_HP(xtarget, XY, Tlow, Thigh,
                              estimateEquil, printLvl, err, maxsteps, loglevel);
    } else if (XY == SP) {
        xtarget = m_mix->entropy();
        double Tlow = 0.5 * m_mix->minTemp();
        double Thigh = 2.0 * m_mix->maxTemp();
        return equilibrate_SP(xtarget, Tlow, Thigh,
                              estimateEquil, printLvl, err, maxsteps, loglevel);
    } else if (XY == TV) {
        xtarget = m_mix->temperature();
        return equilibrate_TV(XY, xtarget,
                              estimateEquil, printLvl, err, maxsteps, loglevel);
    } else if (XY == HV) {
        xtarget = m_mix->enthalpy();
        return equilibrate_TV(XY, xtarget,
                              estimateEquil, printLvl, err, maxsteps, loglevel);
    } else if (XY == UV) {
        xtarget = m_mix->IntEnergy();
        return equilibrate_TV(XY, xtarget,
                              estimateEquil, printLvl, err, maxsteps, loglevel);
    } else if (XY == SV) {
        xtarget = m_mix->entropy();
        return equilibrate_TV(XY, xtarget, estimateEquil,
                                  printLvl, err, maxsteps, loglevel);
    } else {
        throw CanteraError("vcs_MultiPhaseEquil::equilibrate",
                           "Unsupported Option");
    }
}
 
int vcs_MultiPhaseEquil::equilibrate_TP(int estimateEquil, int printLvl, double err,
                                        int maxsteps, int loglevel)
{
    int maxit = maxsteps;
    clockWC tickTock;
    m_printLvl = printLvl;
    m_vsolve.m_printLvl = printLvl;
    m_vsolve.m_doEstimateEquil = estimateEquil;
 
    // Check obvious bounds on the temperature and pressure NOTE, we may want to
    // do more here with the real bounds given by the ThermoPhase objects.
    if (m_mix->temperature() <= 0.0) {
        throw CanteraError("vcs_MultiPhaseEquil::equilibrate_TP",
                           "Temperature less than zero on input");
    }
    if (m_mix->pressure() <= 0.0) {
        throw CanteraError("vcs_MultiPhaseEquil::equilibrate_TP",
                           "Pressure less than zero on input");
    }
 
    //! Call the thermo Program
    int ip1 = m_printLvl;
    int ipr = std::max(0, m_printLvl-1);
    if (m_printLvl >= 3) {
        ip1 = m_printLvl - 2;
    } else {
        ip1 = 0;
    }
    int iSuccess = m_vsolve.vcs(ipr, ip1, maxit);
 
    double te = tickTock.secondsWC();
    if (printLvl > 0) {
        vector<double> mu(m_mix->nSpecies());
        m_mix->getChemPotentials(mu.data());
        plogf("\n Results from vcs:\n");
        if (iSuccess != 0) {
            plogf("\nVCS FAILED TO CONVERGE!\n");
        }
        plogf("\n");
        plogf("Temperature = %g Kelvin\n", m_vsolve.m_temperature);
        plogf("Pressure    = %g Pa\n", m_vsolve.m_pressurePA);
        plogf("\n");
        plogf("----------------------------------------"
              "---------------------\n");
        plogf(" Name             Mole_Number(kmol)");
        plogf("  Mole_Fraction     Chem_Potential (J/kmol)\n");
        plogf("--------------------------------------------------"
              "-----------\n");
        for (size_t i = 0; i < m_mix->nSpecies(); i++) {
            plogf("%-12s", m_mix->speciesName(i));
            if (m_vsolve.m_speciesUnknownType[i] == VCS_SPECIES_TYPE_INTERFACIALVOLTAGE) {
                plogf("  %15.3e %15.3e  ", 0.0, m_mix->moleFraction(i));
                plogf("%15.3e\n", mu[i]);
            } else {
                plogf("  %15.3e   %15.3e  ", m_mix->speciesMoles(i), m_mix->moleFraction(i));
                if (m_mix->speciesMoles(i) <= 0.0) {
                    size_t iph = m_vsolve.m_phaseID[i];
                    vcs_VolPhase* VPhase = m_vsolve.m_VolPhaseList[iph].get();
                    if (VPhase->nSpecies() > 1) {
                        plogf("     -1.000e+300\n");
                    } else {
                        plogf("%15.3e\n", mu[i]);
                    }
                } else {
                    plogf("%15.3e\n", mu[i]);
                }
            }
        }
        plogf("------------------------------------------"
              "-------------------\n");
        if (printLvl > 2 && m_vsolve.m_timing_print_lvl > 0) {
            plogf("Total time = %12.6e seconds\n", te);
        }
    }
    return iSuccess;
}
 
void vcs_MultiPhaseEquil::reportCSV(const string& reportFile)
{
    size_t nphase = m_vsolve.m_numPhases;
 
    FILE* FP = fopen(reportFile.c_str(), "w");
    if (!FP) {
        throw CanteraError("vcs_MultiPhaseEquil::reportCSV",
                           "Failure to open file");
    }
    vector<double> VolPM;
    vector<double> activity;
    vector<double> ac;
    vector<double> mu;
    vector<double> mu0;
    vector<double> molalities;
 
    double vol = 0.0;
    for (size_t iphase = 0; iphase < nphase; iphase++) {
        ThermoPhase& tref = m_mix->phase(iphase);
        size_t nSpecies = tref.nSpecies();
        VolPM.resize(nSpecies, 0.0);
        tref.getPartialMolarVolumes(&VolPM[0]);
        vcs_VolPhase* volP = m_vsolve.m_VolPhaseList[iphase].get();
 
        double TMolesPhase = volP->totalMoles();
        double VolPhaseVolumes = 0.0;
        for (size_t k = 0; k < nSpecies; k++) {
            VolPhaseVolumes += VolPM[k] * tref.moleFraction(k);
        }
        VolPhaseVolumes *= TMolesPhase;
        vol += VolPhaseVolumes;
    }
 
    fprintf(FP,"--------------------- VCS_MULTIPHASE_EQUIL FINAL REPORT"
            " -----------------------------\n");
    fprintf(FP,"Temperature  = %11.5g kelvin\n", m_mix->temperature());
    fprintf(FP,"Pressure     = %11.5g Pascal\n", m_mix->pressure());
    fprintf(FP,"Total Volume = %11.5g m**3\n", vol);
    fprintf(FP,"Number Basis optimizations = %d\n", m_vsolve.m_VCount->Basis_Opts);
    fprintf(FP,"Number VCS iterations = %d\n", m_vsolve.m_VCount->Its);
 
    for (size_t iphase = 0; iphase < nphase; iphase++) {
        ThermoPhase& tref = m_mix->phase(iphase);
        string phaseName = tref.name();
        vcs_VolPhase* volP = m_vsolve.m_VolPhaseList[iphase].get();
        double TMolesPhase = volP->totalMoles();
        size_t nSpecies = tref.nSpecies();
        activity.resize(nSpecies, 0.0);
        ac.resize(nSpecies, 0.0);
        mu0.resize(nSpecies, 0.0);
        mu.resize(nSpecies, 0.0);
        VolPM.resize(nSpecies, 0.0);
        molalities.resize(nSpecies, 0.0);
        int actConvention = tref.activityConvention();
        tref.getActivities(&activity[0]);
        tref.getActivityCoefficients(&ac[0]);
        tref.getStandardChemPotentials(&mu0[0]);
        tref.getPartialMolarVolumes(&VolPM[0]);
        tref.getChemPotentials(&mu[0]);
        double VolPhaseVolumes = 0.0;
        for (size_t k = 0; k < nSpecies; k++) {
            VolPhaseVolumes += VolPM[k] * tref.moleFraction(k);
        }
        VolPhaseVolumes *= TMolesPhase;
        vol += VolPhaseVolumes;
 
        if (actConvention == 1) {
            MolalityVPSSTP* mTP = static_cast<MolalityVPSSTP*>(&tref);
            mTP->getMolalities(&molalities[0]);
            tref.getChemPotentials(&mu[0]);
 
            if (iphase == 0) {
                fprintf(FP,"        Name,      Phase,  PhaseMoles,  Mole_Fract, "
                        "Molalities,  ActCoeff,   Activity,"
                        "ChemPot_SS0,   ChemPot,   mole_num,       PMVol, Phase_Volume\n");
 
                fprintf(FP,"            ,           ,      (kmol),            , "
                        "          ,          ,           ,"
                        "   (J/kmol),  (J/kmol),     (kmol), (m**3/kmol),     (m**3)\n");
            }
            for (size_t k = 0; k < nSpecies; k++) {
                string sName = tref.speciesName(k);
                fprintf(FP,"%12s, %11s, %11.3e, %11.3e, %11.3e, %11.3e, %11.3e,"
                        "%11.3e, %11.3e, %11.3e, %11.3e, %11.3e\n",
                        sName.c_str(),
                        phaseName.c_str(), TMolesPhase,
                        tref.moleFraction(k), molalities[k], ac[k], activity[k],
                        mu0[k]*1.0E-6, mu[k]*1.0E-6,
                        tref.moleFraction(k) * TMolesPhase,
                        VolPM[k], VolPhaseVolumes);
            }
        } else {
            if (iphase == 0) {
                fprintf(FP,"        Name,       Phase,  PhaseMoles,  Mole_Fract,  "
                        "Molalities,   ActCoeff,    Activity,"
                        "  ChemPotSS0,     ChemPot,   mole_num,       PMVol, Phase_Volume\n");
 
                fprintf(FP,"            ,            ,      (kmol),            ,  "
                        "          ,           ,            ,"
                        "    (J/kmol),    (J/kmol),     (kmol), (m**3/kmol),       (m**3)\n");
            }
            for (size_t k = 0; k < nSpecies; k++) {
                molalities[k] = 0.0;
            }
            for (size_t k = 0; k < nSpecies; k++) {
                string sName = tref.speciesName(k);
                fprintf(FP,"%12s, %11s, %11.3e, %11.3e, %11.3e, %11.3e, %11.3e, "
                        "%11.3e, %11.3e,% 11.3e, %11.3e, %11.3e\n",
                        sName.c_str(),
                        phaseName.c_str(), TMolesPhase,
                        tref.moleFraction(k), molalities[k], ac[k],
                        activity[k], mu0[k]*1.0E-6, mu[k]*1.0E-6,
                        tref.moleFraction(k) * TMolesPhase,
                        VolPM[k], VolPhaseVolumes);
            }
        }
    }
    fclose(FP);
}
 
}