PDSS_HKFT.cpp

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/**
 *  @file PDSS_HKFT.cpp
 *    Definitions for the class PDSS_HKFT (pressure dependent standard state)
 *    which handles calculations for a single species in a phase using the
 *    HKFT standard state
 *    (see \ref pdssthermo and class \link Cantera::PDSS_HKFT PDSS_HKFT\endlink).
 */
/*
 * Copyright (2006) Sandia Corporation. Under the terms of
 * Contract DE-AC04-94AL85000 with Sandia Corporation, the
 * U.S. Government retains certain rights in this software.
 */

#include "cantera/base/ctml.h"
#include "cantera/thermo/PDSS_HKFT.h"
#include "cantera/thermo/PDSS_Water.h"
#include "cantera/thermo/VPStandardStateTP.h"
#include "cantera/base/stringUtils.h"

#include <fstream>

using namespace std;

namespace Cantera
{
/*
 *  Set the default to error exit if there is an input file inconsistency
 */
int PDSS_HKFT::s_InputInconsistencyErrorExit = 1;

PDSS_HKFT::PDSS_HKFT(VPStandardStateTP* tp, size_t spindex) :
    PDSS(tp, spindex),
    m_waterSS(0),
    m_densWaterSS(-1.0),
    m_waterProps(0),
    m_born_coeff_j(-1.0),
    m_r_e_j(-1.0),
    m_deltaG_formation_tr_pr(0.0),
    m_deltaH_formation_tr_pr(0.0),
    m_Mu0_tr_pr(0.0),
    m_Entrop_tr_pr(0.0),
    m_a1(0.0),
    m_a2(0.0),
    m_a3(0.0),
    m_a4(0.0),
    m_c1(0.0),
    m_c2(0.0),
    m_omega_pr_tr(0.0),
    m_Y_pr_tr(0.0),
    m_Z_pr_tr(0.0),
    m_presR_bar(0.0),
    m_domega_jdT_prtr(0.0),
    m_charge_j(0.0)
{
    m_pres = OneAtm;
    m_pdssType = cPDSS_MOLAL_HKFT;
    m_presR_bar = OneAtm * 1.0E-5;
    m_presR_bar = 1.0;
}

PDSS_HKFT::PDSS_HKFT(VPStandardStateTP* tp, size_t spindex,
                     const std::string& inputFile, const std::string& id) :
    PDSS(tp, spindex),
    m_waterSS(0),
    m_densWaterSS(-1.0),
    m_waterProps(0),
    m_born_coeff_j(-1.0),
    m_r_e_j(-1.0),
    m_deltaG_formation_tr_pr(0.0),
    m_deltaH_formation_tr_pr(0.0),
    m_Mu0_tr_pr(0.0),
    m_Entrop_tr_pr(0.0),
    m_a1(0.0),
    m_a2(0.0),
    m_a3(0.0),
    m_a4(0.0),
    m_c1(0.0),
    m_c2(0.0),
    m_omega_pr_tr(0.0),
    m_Y_pr_tr(0.0),
    m_Z_pr_tr(0.0),
    m_presR_bar(1.0),
    m_domega_jdT_prtr(0.0),
    m_charge_j(0.0)
{
    m_pres = OneAtm;
    m_pdssType = cPDSS_MOLAL_HKFT;
    m_presR_bar = OneAtm * 1.0E-5;
    m_presR_bar = 1.0;
    constructPDSSFile(tp, spindex, inputFile, id);
}

PDSS_HKFT::PDSS_HKFT(VPStandardStateTP* tp, size_t spindex, const XML_Node& speciesNode,
                     const XML_Node& phaseRoot, bool spInstalled) :
    PDSS(tp, spindex),
    m_waterSS(0),
    m_densWaterSS(-1.0),
    m_waterProps(0),
    m_born_coeff_j(-1.0),
    m_r_e_j(-1.0),
    m_deltaG_formation_tr_pr(0.0),
    m_deltaH_formation_tr_pr(0.0),
    m_Mu0_tr_pr(0.0),
    m_Entrop_tr_pr(0.0),
    m_a1(0.0),
    m_a2(0.0),
    m_a3(0.0),
    m_a4(0.0),
    m_c1(0.0),
    m_c2(0.0),
    m_omega_pr_tr(0.0),
    m_Y_pr_tr(0.0),
    m_Z_pr_tr(0.0),
    m_presR_bar(0.0),
    m_domega_jdT_prtr(0.0),
    m_charge_j(0.0)
{
    m_pres = OneAtm;
    m_pdssType = cPDSS_MOLAL_HKFT;
    m_presR_bar = OneAtm * 1.0E-5;
    m_presR_bar = 1.0;
    // We have to read the info from here
    constructPDSSXML(tp, spindex, speciesNode, phaseRoot, spInstalled);
}

PDSS_HKFT::PDSS_HKFT(const PDSS_HKFT& b) :
    PDSS(b),
    m_waterSS(0),
    m_densWaterSS(-1.0),
    m_waterProps(0),
    m_born_coeff_j(-1.0),
    m_r_e_j(-1.0),
    m_deltaG_formation_tr_pr(0.0),
    m_deltaH_formation_tr_pr(0.0),
    m_Mu0_tr_pr(0.0),
    m_Entrop_tr_pr(0.0),
    m_a1(0.0),
    m_a2(0.0),
    m_a3(0.0),
    m_a4(0.0),
    m_c1(0.0),
    m_c2(0.0),
    m_omega_pr_tr(0.0),
    m_Y_pr_tr(0.0),
    m_Z_pr_tr(0.0),
    m_presR_bar(0.0),
    m_domega_jdT_prtr(0.0),
    m_charge_j(0.0)
{
    m_pdssType = cPDSS_MOLAL_HKFT;
    m_presR_bar = OneAtm * 1.0E-5;
    /*
     * Use the assignment operator to do the brunt
     * of the work for the copy constructor.
     */
    *this = b;
}

PDSS_HKFT& PDSS_HKFT::operator=(const PDSS_HKFT& b)
{
    if (&b == this) {
        return *this;
    }
    /*
     * Call the base class operator
     */
    PDSS::operator=(b);

    //! Need to call initAllPtrs AFTER, to get the correct m_waterSS
    m_waterSS        = 0;
    m_densWaterSS               = b.m_densWaterSS;
    //! Need to call initAllPtrs AFTER, to get the correct m_waterProps
    delete m_waterProps;
    m_waterProps                = 0;
    m_born_coeff_j              = b.m_born_coeff_j;
    m_r_e_j                     = b.m_r_e_j;
    m_deltaG_formation_tr_pr    = b.m_deltaG_formation_tr_pr;
    m_deltaH_formation_tr_pr    = b.m_deltaH_formation_tr_pr;
    m_Mu0_tr_pr                 = b.m_Mu0_tr_pr;
    m_Entrop_tr_pr              = b.m_Entrop_tr_pr;
    m_a1                        = b.m_a1;
    m_a2                        = b.m_a2;
    m_a3                        = b.m_a3;
    m_a4                        = b.m_a4;
    m_c1                        = b.m_c1;
    m_c2                        = b.m_c2;
    m_omega_pr_tr               = b.m_omega_pr_tr;
    m_Y_pr_tr                   = b.m_Y_pr_tr;
    m_Z_pr_tr                   = b.m_Z_pr_tr;
    m_presR_bar                 = b.m_presR_bar;
    m_domega_jdT_prtr           = b.m_domega_jdT_prtr;
    m_charge_j                  = b.m_charge_j;

    // Here we just fill these in so that local copies within the VPSS object work.
    m_waterSS                  = b.m_waterSS;
    m_waterProps               = new WaterProps(m_waterSS);

    return *this;
}

PDSS_HKFT::~PDSS_HKFT()
{
    delete m_waterProps;
}

PDSS* PDSS_HKFT::duplMyselfAsPDSS() const
{
    return new PDSS_HKFT(*this);
}

doublereal PDSS_HKFT::enthalpy_mole() const
{
    // Ok we may change this evaluation method in the future.
    doublereal h = gibbs_mole() + m_temp * entropy_mole();

#ifdef DEBUG_MODE_NOT
    doublereal h2 = enthalpy_mole2();
    if (fabs(h - h2) > 1.0E-1) {
        printf("we are here, h = %g, h2 = %g, k = %d, T = %g, P = %g p0 = %g\n",
               h, h2, m_spindex, m_temp, m_pres,
               m_p0);
    }
#endif
    return h;
}

#ifdef DEBUG_MODE
doublereal PDSS_HKFT::enthalpy_mole2() const
{
    double enthTRPR = m_Mu0_tr_pr + 298.15 * m_Entrop_tr_pr * 1.0E3 * 4.184;
    return deltaH() + enthTRPR;
}
#endif

doublereal PDSS_HKFT::intEnergy_mole() const
{
    return enthalpy_RT() - molarVolume() * m_pres;
}

doublereal PDSS_HKFT::entropy_mole() const
{
    return m_Entrop_tr_pr * 1.0E3 * 4.184 + deltaS();
}

doublereal PDSS_HKFT::gibbs_mole() const
{
    return m_Mu0_tr_pr + deltaG();
}

doublereal PDSS_HKFT::cp_mole() const
{
    doublereal pbar = m_pres * 1.0E-5;
    doublereal c1term = m_c1;

    doublereal c2term = m_c2 / (m_temp - 228.) / (m_temp - 228.);

    doublereal a3term = -m_a3 / (m_temp - 228.) / (m_temp - 228.) / (m_temp - 228.) * 2.0 * m_temp * (pbar - m_presR_bar);

    doublereal a4term = -m_a4 / (m_temp - 228.) / (m_temp - 228.) / (m_temp - 228.) * 2.0 * m_temp
                        * log((2600. + pbar)/(2600. + m_presR_bar));

    doublereal omega_j;
    doublereal domega_jdT;
    doublereal d2omega_jdT2;
    if (m_charge_j == 0.0) {
        omega_j = m_omega_pr_tr;
        domega_jdT = 0.0;
        d2omega_jdT2 = 0.0;
    } else {
        doublereal nu = 166027;
        doublereal r_e_j_pr_tr = m_charge_j * m_charge_j / (m_omega_pr_tr/nu + m_charge_j/3.082);

        doublereal gval = gstar(m_temp, m_pres, 0);

        doublereal dgvaldT = gstar(m_temp, m_pres, 1);
        doublereal d2gvaldT2 = gstar(m_temp, m_pres, 2);

        doublereal r_e_j = r_e_j_pr_tr + fabs(m_charge_j) * gval;
        doublereal dr_e_jdT = fabs(m_charge_j) * dgvaldT;
        doublereal d2r_e_jdT2 =  fabs(m_charge_j) * d2gvaldT2;

        doublereal r_e_j2 = r_e_j * r_e_j;

        doublereal charge2 = m_charge_j * m_charge_j;

        doublereal r_e_H = 3.082 + gval;
        doublereal r_e_H2 = r_e_H * r_e_H;

        omega_j = nu * (charge2 / r_e_j - m_charge_j / r_e_H);

        domega_jdT =  nu * (-(charge2    / r_e_j2 * dr_e_jdT)
                            +(m_charge_j / r_e_H2 * dgvaldT));

        d2omega_jdT2 = nu * (2.0*charge2*dr_e_jdT*dr_e_jdT/(r_e_j2*r_e_j) - charge2*d2r_e_jdT2/r_e_j2
                             -2.0*m_charge_j*dgvaldT*dgvaldT/(r_e_H2*r_e_H) + m_charge_j*d2gvaldT2 /r_e_H2);
    }

    doublereal relepsilon = m_waterProps->relEpsilon(m_temp, m_pres, 0);
    doublereal drelepsilondT = m_waterProps->relEpsilon(m_temp, m_pres, 1);

    doublereal Y = drelepsilondT / (relepsilon * relepsilon);

    doublereal d2relepsilondT2 = m_waterProps->relEpsilon(m_temp, m_pres, 2);

#ifdef DEBUG_MODE_NOT
    doublereal d1 = m_waterProps->relEpsilon(m_temp, m_pres, 1);
    doublereal d2 = m_waterProps->relEpsilon(m_temp + 0.0001, m_pres, 1);
    doublereal d3 = (d2 - d1) / 0.0001;
    if (fabs(d2relepsilondT2 - d3) > 1.0E-6) {
        printf("we are here\n");
    }
#endif

    doublereal X = d2relepsilondT2 / (relepsilon* relepsilon) - 2.0 * relepsilon * Y * Y;

    doublereal Z = -1.0 / relepsilon;

    doublereal yterm = 2.0 * m_temp * Y * domega_jdT;

    doublereal xterm = omega_j * m_temp * X;

    doublereal otterm = m_temp * d2omega_jdT2 * (Z + 1.0);

    doublereal rterm =  - m_domega_jdT_prtr * (m_Z_pr_tr + 1.0);

    doublereal Cp_calgmol = c1term + c2term + a3term + a4term + yterm + xterm + otterm + rterm;

    // Convert to Joules / kmol
    doublereal Cp = Cp_calgmol * 1.0E3 * 4.184;

#ifdef DEBUG_MODE_NOT
    double e1 = enthalpy_mole();
    m_temp = m_temp - 0.001;
    double e2 = enthalpy_mole();
    m_temp = m_temp + 0.001;
    double cpd = (e1 - e2) / 0.001;
    if (fabs(Cp - cpd) > 10.0) {
        printf("Cp difference : raw: %g, delta: %g, k = %d, T = %g, m_pres = %g\n",
               Cp, cpd, m_spindex, m_temp, m_pres);
    }
#endif
    return Cp;
}

doublereal  PDSS_HKFT::molarVolume() const
{
    // Initially do all calculations in (cal/gmol/Pa)

    doublereal a1term = m_a1 * 1.0E-5;

    doublereal a2term = m_a2 / (2600.E5 + m_pres);

    doublereal a3term = m_a3 * 1.0E-5/ (m_temp - 228.);

    doublereal a4term = m_a4 / (m_temp - 228.) / (2600.E5 + m_pres);

    doublereal omega_j;
    doublereal domega_jdP;
    if (m_charge_j == 0.0) {
        omega_j = m_omega_pr_tr;
        domega_jdP = 0.0;
    } else {
        doublereal nu = 166027.;
        doublereal charge2 = m_charge_j * m_charge_j;
        doublereal r_e_j_pr_tr = charge2 / (m_omega_pr_tr/nu + m_charge_j/3.082);

        doublereal gval    = gstar(m_temp, m_pres, 0);
        doublereal dgvaldP = gstar(m_temp, m_pres, 3);

        doublereal r_e_j = r_e_j_pr_tr + fabs(m_charge_j) * gval;
        doublereal r_e_H = 3.082 + gval;

        omega_j = nu * (charge2 / r_e_j - m_charge_j / r_e_H);

        doublereal dr_e_jdP = fabs(m_charge_j) * dgvaldP;

        domega_jdP = -  nu * (charge2 / (r_e_j * r_e_j) * dr_e_jdP)
                     + nu * m_charge_j / (r_e_H * r_e_H) * dgvaldP;
    }

    doublereal drelepsilondP = m_waterProps->relEpsilon(m_temp, m_pres, 3);

    doublereal relepsilon = m_waterProps->relEpsilon(m_temp, m_pres, 0);

    doublereal Q = drelepsilondP / (relepsilon * relepsilon);

    doublereal Z = -1.0 / relepsilon;

    doublereal wterm = - domega_jdP * (Z + 1.0);

    doublereal qterm = - omega_j * Q;

    doublereal molVol_calgmolPascal = a1term + a2term +  a3term + a4term + wterm + qterm;

    // Convert to m**3 / kmol from (cal/gmol/Pa)
    return molVol_calgmolPascal * 4.184 * 1.0E3;
}

doublereal
PDSS_HKFT::density() const
{
    return m_mw / molarVolume();
}

doublereal
PDSS_HKFT::gibbs_RT_ref() const
{
    doublereal m_psave = m_pres;
    m_pres = m_waterSS->pref_safe(m_temp);
    doublereal ee = gibbs_RT();
    m_pres = m_psave;
    return ee;
}

doublereal
PDSS_HKFT::enthalpy_RT_ref() const
{
    doublereal m_psave = m_pres;
    m_pres = m_waterSS->pref_safe(m_temp);
    doublereal hh = enthalpy_RT();
    m_pres = m_psave;
    return hh;
}

doublereal
PDSS_HKFT::entropy_R_ref() const
{
    doublereal m_psave = m_pres;
    m_pres = m_waterSS->pref_safe(m_temp);
    doublereal ee = entropy_R();
    m_pres = m_psave;
    return ee;
}

doublereal
PDSS_HKFT::cp_R_ref() const
{
    doublereal m_psave = m_pres;
    m_pres = m_waterSS->pref_safe(m_temp);
    doublereal ee = cp_R();
    m_pres = m_psave;
    return ee;
}

doublereal
PDSS_HKFT::molarVolume_ref() const
{
    doublereal m_psave = m_pres;
    m_pres = m_waterSS->pref_safe(m_temp);
    doublereal ee = molarVolume();
    m_pres = m_psave;
    return ee;
}

void PDSS_HKFT::setState_TP(doublereal temp, doublereal pres)
{
    setTemperature(temp);
    setPressure(pres);
}

void PDSS_HKFT::initThermo()
{
    PDSS::initThermo();

    m_waterSS = dynamic_cast<PDSS_Water*>(m_tp->providePDSS(0));
    /*
     *  Section to initialize  m_Z_pr_tr and   m_Y_pr_tr
     */
    m_temp = 273.15 + 25.;
    m_pres = OneAtm;
    doublereal relepsilon = m_waterProps->relEpsilon(m_temp, m_pres, 0);

    m_waterSS->setState_TP(m_temp, m_pres);
    m_densWaterSS = m_waterSS->density();
    m_Z_pr_tr = -1.0 / relepsilon;

    doublereal drelepsilondT = m_waterProps->relEpsilon(m_temp, m_pres, 1);

    m_Y_pr_tr = drelepsilondT / (relepsilon * relepsilon);

    m_waterProps = new WaterProps(m_waterSS);

    m_presR_bar = OneAtm / 1.0E5;
    m_presR_bar = 1.0;
    m_charge_j = m_tp->charge(m_spindex);
    convertDGFormation();

    //! Ok, we have mu. Let's check it against the input value
    // of DH_F to see that we have some internal consistency

    doublereal Hcalc = m_Mu0_tr_pr + 298.15 * (m_Entrop_tr_pr * 1.0E3 * 4.184);

    doublereal DHjmol = m_deltaH_formation_tr_pr * 1.0E3 * 4.184;

    // If the discrepancy is greater than 100 cal gmol-1, print
    // an error and exit.
    if (fabs(Hcalc -DHjmol) > 100.* 1.0E3 * 4.184) {
        std::string sname = m_tp->speciesName(m_spindex);
        if (s_InputInconsistencyErrorExit) {

            throw CanteraError(" PDSS_HKFT::initThermo() for " + sname,
                               "DHjmol is not consistent with G and S: " +
                               fp2str(Hcalc/(4.184E3)) + " vs "
                               + fp2str(m_deltaH_formation_tr_pr) + "cal gmol-1");
        } else {
            writelog(" PDSS_HKFT::initThermo() WARNING: "
                     "DHjmol for " + sname + " is not consistent with G and S: calculated " +
                     fp2str(Hcalc/(4.184E3)) + " vs input "
                        + fp2str(m_deltaH_formation_tr_pr) + "cal gmol-1");
            writelog("                                : continuing with consistent DHjmol = " + fp2str(Hcalc/(4.184E3)));
            m_deltaH_formation_tr_pr = Hcalc / (1.0E3 * 4.184);
        }
    }
    doublereal nu = 166027;

    doublereal r_e_j_pr_tr;
    if (m_charge_j != 0.0) {
        r_e_j_pr_tr = m_charge_j * m_charge_j / (m_omega_pr_tr/nu + m_charge_j/3.082);
    } else {
        r_e_j_pr_tr = 0.0;
    }

    if (m_charge_j == 0.0) {
        m_domega_jdT_prtr = 0.0;
    } else {
        doublereal gval = gstar(m_temp, m_pres, 0);

        doublereal dgvaldT = gstar(m_temp, m_pres, 1);

        doublereal r_e_j = r_e_j_pr_tr + fabs(m_charge_j) * gval;
        doublereal dr_e_jdT = fabs(m_charge_j) * dgvaldT;

        m_domega_jdT_prtr =  -  nu * (m_charge_j * m_charge_j / (r_e_j * r_e_j) * dr_e_jdT)
                             + nu * m_charge_j / (3.082 + gval) / (3.082 + gval) * dgvaldT;
    }
}

void PDSS_HKFT::initAllPtrs(VPStandardStateTP* vptp_ptr, VPSSMgr* vpssmgr_ptr,
                            SpeciesThermo* spthermo_ptr)
{
    PDSS::initAllPtrs(vptp_ptr, vpssmgr_ptr,  spthermo_ptr);
    m_waterSS = dynamic_cast<PDSS_Water*>(m_tp->providePDSS(0));
    delete m_waterProps;
    m_waterProps = new WaterProps(m_waterSS);
}

void PDSS_HKFT::constructPDSSXML(VPStandardStateTP* tp, size_t spindex,
                                 const XML_Node& speciesNode,
                                 const XML_Node& phaseNode, bool spInstalled)
{
    int hasDGO = 0;
    int hasSO = 0;
    int hasDHO = 0;

    if (!spInstalled) {
        throw CanteraError("PDSS_HKFT::constructPDSSXML", "spInstalled false not handled");
    }

    const XML_Node* tn = speciesNode.findByName("thermo");
    if (!tn) {
        throw CanteraError("PDSS_HKFT::constructPDSSXML",
                           "no thermo Node for species " + speciesNode.name());
    }
    if (lowercase(tn->attrib("model")) != "hkft") {
        throw CanteraError("PDSS_HKFT::initThermoXML",
                           "thermo model for species isn't hkft: "
                           + speciesNode.name());
    }
    const XML_Node* hh = tn->findByName("HKFT");
    if (!hh) {
        throw CanteraError("PDSS_HKFT::constructPDSSXML",
                           "no Thermo::HKFT Node for species " + speciesNode.name());
    }

    // go get the attributes
    m_p0 = OneAtm;
    std::string p0string = hh->attrib("Pref");
    if (p0string != "") {
        m_p0 = strSItoDbl(p0string);
    }

    std::string minTstring = hh->attrib("Tmin");
    if (minTstring != "") {
        m_minTemp = fpValueCheck(minTstring);
    }

    std::string maxTstring = hh->attrib("Tmax");
    if (maxTstring != "") {
        m_maxTemp = fpValueCheck(maxTstring);
    }

    if (hh->hasChild("DG0_f_Pr_Tr")) {
        doublereal val = getFloat(*hh, "DG0_f_Pr_Tr");
        m_deltaG_formation_tr_pr = val;
        hasDGO = 1;
    }

    if (hh->hasChild("DH0_f_Pr_Tr")) {
        doublereal val = getFloat(*hh, "DH0_f_Pr_Tr");
        m_deltaH_formation_tr_pr = val;
        hasDHO = 1;
    }

    if (hh->hasChild("S0_Pr_Tr")) {
        doublereal val = getFloat(*hh, "S0_Pr_Tr");
        m_Entrop_tr_pr= val;
        hasSO = 1;
    }

    const XML_Node* ss = speciesNode.findByName("standardState");
    if (!ss) {
        throw CanteraError("PDSS_HKFT::constructPDSSXML",
                           "no standardState Node for species " + speciesNode.name());
    }
    if (lowercase(ss->attrib("model")) != "hkft") {
        throw CanteraError("PDSS_HKFT::initThermoXML",
                           "standardState model for species isn't hkft: "
                           + speciesNode.name());
    }
    if (ss->hasChild("a1")) {
        m_a1 = getFloat(*ss, "a1");
    } else {
        throw CanteraError("PDSS_HKFT::constructPDSSXML", " missing a1 field");
    }
    if (ss->hasChild("a2")) {
        m_a2 = getFloat(*ss, "a2");
    } else {
        throw CanteraError("PDSS_HKFT::constructPDSSXML", " missing a2 field");
    }
    if (ss->hasChild("a3")) {
        m_a3 = getFloat(*ss, "a3");
    } else {
        throw CanteraError("PDSS_HKFT::constructPDSSXML", " missing a3 field");
    }
    if (ss->hasChild("a4")) {
        m_a4 = getFloat(*ss, "a4");
    } else {
        throw CanteraError("PDSS_HKFT::constructPDSSXML", " missing a4 field");
    }

    if (ss->hasChild("c1")) {
        m_c1 = getFloat(*ss, "c1");
    } else {
        throw CanteraError("PDSS_HKFT::constructPDSSXML", " missing c1 field");
    }
    if (ss->hasChild("c2")) {
        m_c2 = getFloat(*ss, "c2");
    } else {
        throw CanteraError("PDSS_HKFT::constructPDSSXML", " missing c2 field");
    }
    if (ss->hasChild("omega_Pr_Tr")) {
        m_omega_pr_tr = getFloat(*ss, "omega_Pr_Tr");
    } else {
        throw CanteraError("PDSS_HKFT::constructPDSSXML", " missing omega_Pr_Tr field");
    }


    int isum = hasDGO + hasDHO + hasSO;
    if (isum < 2) {
        throw CanteraError("PDSS_HKFT::constructPDSSXML",
                           "Missing 2 or more of DG0_f_Pr_Tr, DH0_f_Pr_Tr, or S0_f_Pr_Tr fields. "
                           "Need to supply at least two of these fields");
    }
    // Ok, if we are missing one, then we construct its value from the other two.
    // This code has been internally verified.
    if (hasDHO == 0) {
        m_charge_j = m_tp->charge(m_spindex);
        convertDGFormation();
        doublereal Hcalc = m_Mu0_tr_pr + 298.15 * (m_Entrop_tr_pr * 1.0E3 * 4.184);
        m_deltaH_formation_tr_pr = Hcalc / (1.0E3 * 4.184);
    }
    if (hasDGO == 0) {
        doublereal DHjmol = m_deltaH_formation_tr_pr * 1.0E3 * 4.184;
        m_Mu0_tr_pr = DHjmol -  298.15 * (m_Entrop_tr_pr * 1.0E3 * 4.184);
        m_deltaG_formation_tr_pr =   m_Mu0_tr_pr / (1.0E3 * 4.184);
        double tmp =   m_Mu0_tr_pr;
        m_charge_j = m_tp->charge(m_spindex);
        convertDGFormation();
        double totalSum =  m_Mu0_tr_pr - tmp;
        m_Mu0_tr_pr = tmp;
        m_deltaG_formation_tr_pr = (m_Mu0_tr_pr - totalSum)/ (1.0E3 * 4.184);
    }
    if (hasSO == 0) {
        m_charge_j = m_tp->charge(m_spindex);
        convertDGFormation();
        doublereal DHjmol = m_deltaH_formation_tr_pr * 1.0E3 * 4.184;
        m_Entrop_tr_pr = (DHjmol - m_Mu0_tr_pr) / (298.15 * 1.0E3 * 4.184);
    }

}

void PDSS_HKFT::constructPDSSFile(VPStandardStateTP* tp, size_t spindex,
                                  const std::string& inputFile,
                                  const std::string& id)
{
    if (inputFile.size() == 0) {
        throw CanteraError("PDSS_HKFT::initThermo",
                           "input file is null");
    }
    std::string path = findInputFile(inputFile);
    ifstream fin(path.c_str());
    if (!fin) {
        throw CanteraError("PDSS_HKFT::initThermo","could not open "
                           +path+" for reading.");
    }
    /*
     * The phase object automatically constructs an XML object.
     * Use this object to store information.
     */

    XML_Node fxml;
    fxml.build(fin);
    XML_Node* fxml_phase = findXMLPhase(&fxml, id);
    if (!fxml_phase) {
        throw CanteraError("PDSS_HKFT::initThermo",
                           "ERROR: Can not find phase named " +
                           id + " in file named " + inputFile);
    }

    XML_Node& speciesList = fxml_phase->child("speciesArray");
    XML_Node* speciesDB = get_XML_NameID("speciesData", speciesList["datasrc"],
                                         &(fxml_phase->root()));
    const XML_Node* s =  speciesDB->findByAttr("name", tp->speciesName(spindex));

    constructPDSSXML(tp, spindex, *s, *fxml_phase, true);
}

#ifdef DEBUG_MODE
doublereal PDSS_HKFT::deltaH() const
{
    doublereal pbar = m_pres * 1.0E-5;

    doublereal c1term = m_c1 * (m_temp - 298.15);

    doublereal a1term = m_a1 * (pbar - m_presR_bar);

    doublereal a2term = m_a2 * log((2600. + pbar)/(2600. + m_presR_bar));

    doublereal c2term = -m_c2 * (1.0/(m_temp - 228.) - 1.0/(298.15 - 228.));

    double a3tmp = (2.0 * m_temp - 228.)/ (m_temp - 228.) /(m_temp - 228.);

    doublereal a3term = m_a3 * a3tmp * (pbar - m_presR_bar);

    doublereal a4term = m_a4 * a3tmp * log((2600. + pbar)/(2600. + m_presR_bar));

    doublereal omega_j;
    doublereal  domega_jdT;
    if (m_charge_j == 0.0) {
        omega_j = m_omega_pr_tr;
        domega_jdT = 0.0;
    } else {
        doublereal nu = 166027;
        doublereal r_e_j_pr_tr = m_charge_j * m_charge_j / (m_omega_pr_tr/nu + m_charge_j/3.082);
        doublereal gval = gstar(m_temp, m_pres, 0);
        doublereal r_e_j = r_e_j_pr_tr + fabs(m_charge_j) * gval;

        doublereal dgvaldT = gstar(m_temp, m_pres, 1);
        doublereal dr_e_jdT = fabs(m_charge_j) * dgvaldT;

        omega_j = nu * (m_charge_j * m_charge_j / r_e_j - m_charge_j / (3.082 + gval));

        domega_jdT = -  nu * (m_charge_j * m_charge_j / (r_e_j * r_e_j) * dr_e_jdT)
                     + nu * m_charge_j / (3.082 + gval) / (3.082 + gval) * dgvaldT;
    }

    doublereal relepsilon = m_waterProps->relEpsilon(m_temp, m_pres, 0);
    doublereal drelepsilondT = m_waterProps->relEpsilon(m_temp, m_pres, 1);

    doublereal Y = drelepsilondT / (relepsilon * relepsilon);

    doublereal Z = -1.0 / relepsilon;

    doublereal yterm  =   m_temp * omega_j       * Y;
    doublereal yrterm = - 298.15 * m_omega_pr_tr * m_Y_pr_tr;

    doublereal wterm  = - omega_j * (Z + 1.0);
    doublereal wrterm = + m_omega_pr_tr * (m_Z_pr_tr + 1.0);

    doublereal otterm =    m_temp * domega_jdT        * (Z + 1.0);
    doublereal otrterm = - m_temp * m_domega_jdT_prtr * (m_Z_pr_tr + 1.0);

    doublereal deltaH_calgmol = c1term + a1term + a2term + c2term + a3term + a4term
                                + yterm + yrterm + wterm + wrterm + otterm + otrterm;

    // Convert to Joules / kmol
    return deltaH_calgmol * 1.0E3 * 4.184;
}
#endif
//================================================================================================================
doublereal PDSS_HKFT::deltaG() const
{
    doublereal pbar = m_pres * 1.0E-5;
    doublereal sterm = -  m_Entrop_tr_pr * (m_temp - 298.15);

    doublereal c1term = -m_c1 * (m_temp * log(m_temp/298.15) - (m_temp - 298.15));
    doublereal a1term = m_a1 * (pbar - m_presR_bar);

    doublereal a2term = m_a2 * log((2600. + pbar)/(2600. + m_presR_bar));

    doublereal c2term = -m_c2 * ((1.0/(m_temp - 228.) - 1.0/(298.15 - 228.)) * (228. - m_temp)/228.
                                 - m_temp / (228.*228.) * log((298.15*(m_temp-228.)) / (m_temp*(298.15-228.))));

    doublereal a3term = m_a3 / (m_temp - 228.) * (pbar - m_presR_bar);

    doublereal a4term = m_a4 / (m_temp - 228.) * log((2600. + pbar)/(2600. + m_presR_bar));

    doublereal omega_j;
    if (m_charge_j == 0.0) {
        omega_j = m_omega_pr_tr;
    } else {
        doublereal nu = 166027;
        doublereal r_e_j_pr_tr = m_charge_j * m_charge_j / (m_omega_pr_tr/nu + m_charge_j/3.082);
        doublereal gval = gstar(m_temp, m_pres, 0);
        doublereal r_e_j = r_e_j_pr_tr + fabs(m_charge_j) * gval;
        omega_j = nu * (m_charge_j * m_charge_j / r_e_j - m_charge_j / (3.082 + gval));
    }

    doublereal relepsilon = m_waterProps->relEpsilon(m_temp, m_pres, 0);

    doublereal Z = -1.0 / relepsilon;

    doublereal wterm = - omega_j * (Z + 1.0);

    doublereal wrterm = m_omega_pr_tr * (m_Z_pr_tr + 1.0);

    doublereal yterm = m_omega_pr_tr * m_Y_pr_tr * (m_temp - 298.15);

    doublereal deltaG_calgmol = sterm + c1term + a1term + a2term + c2term + a3term + a4term + wterm + wrterm + yterm;

    // Convert to Joules / kmol
    return deltaG_calgmol * 1.0E3 * 4.184;
}

doublereal PDSS_HKFT::deltaS() const
{
    doublereal pbar = m_pres * 1.0E-5;

    doublereal c1term = m_c1 * log(m_temp/298.15);

    doublereal c2term = -m_c2 / 228. * ((1.0/(m_temp - 228.) - 1.0/(298.15 - 228.))
                                        + 1.0 / 228. * log((298.15*(m_temp-228.)) / (m_temp*(298.15-228.))));

    doublereal a3term = m_a3 / (m_temp - 228.) / (m_temp - 228.) * (pbar - m_presR_bar);

    doublereal a4term = m_a4 / (m_temp - 228.) / (m_temp - 228.) * log((2600. + pbar)/(2600. + m_presR_bar));

    doublereal omega_j;
    doublereal domega_jdT;
    if (m_charge_j == 0.0) {
        omega_j = m_omega_pr_tr;
        domega_jdT = 0.0;
    } else {

        doublereal nu = 166027;
        doublereal r_e_j_pr_tr = m_charge_j * m_charge_j / (m_omega_pr_tr/nu + m_charge_j/3.082);

        doublereal gval = gstar(m_temp, m_pres, 0);

        doublereal dgvaldT = gstar(m_temp, m_pres, 1);

        doublereal r_e_j = r_e_j_pr_tr + fabs(m_charge_j) * gval;
        doublereal dr_e_jdT = fabs(m_charge_j) * dgvaldT;

        omega_j = nu * (m_charge_j * m_charge_j / r_e_j - m_charge_j / (3.082 + gval));

        domega_jdT = -  nu * (m_charge_j * m_charge_j / (r_e_j * r_e_j) * dr_e_jdT)
                     + nu * m_charge_j / (3.082 + gval) / (3.082 + gval) * dgvaldT;
    }

    doublereal relepsilon = m_waterProps->relEpsilon(m_temp, m_pres, 0);
    doublereal drelepsilondT = m_waterProps->relEpsilon(m_temp, m_pres, 1);

    doublereal Y = drelepsilondT / (relepsilon * relepsilon);

    doublereal Z = -1.0 / relepsilon;

    doublereal wterm = omega_j * Y;

    doublereal wrterm = - m_omega_pr_tr * m_Y_pr_tr;

    doublereal otterm = domega_jdT * (Z + 1.0);

    doublereal otrterm = - m_domega_jdT_prtr * (m_Z_pr_tr + 1.0);

    doublereal deltaS_calgmol = c1term + c2term + a3term + a4term + wterm + wrterm  + otterm + otrterm;

    // Convert to Joules / kmol
    return deltaS_calgmol * 1.0E3 * 4.184;
}

doublereal PDSS_HKFT::ag(const doublereal temp, const int ifunc) const
{
    static doublereal ag_coeff[3] = { -2.037662,  5.747000E-3,  -6.557892E-6};
    if (ifunc == 0) {
        return ag_coeff[0] + ag_coeff[1] * temp + ag_coeff[2] * temp * temp;
    } else if (ifunc == 1) {
        return  ag_coeff[1] + ag_coeff[2] * 2.0 * temp;
    }
    if (ifunc != 2) {
        return 0.0;
    }
    return ag_coeff[2] * 2.0;
}

doublereal PDSS_HKFT::bg(const doublereal temp, const int ifunc) const
{
    static doublereal bg_coeff[3] = { 6.107361, -1.074377E-2,  1.268348E-5};
    if (ifunc == 0) {
        return bg_coeff[0] + bg_coeff[1] * temp + bg_coeff[2] * temp * temp;
    }   else if (ifunc == 1) {
        return bg_coeff[1] + bg_coeff[2] * 2.0 * temp;
    }
    if (ifunc != 2) {
        return 0.0;
    }
    return bg_coeff[2] * 2.0;
}

doublereal PDSS_HKFT::f(const doublereal temp, const doublereal pres, const int ifunc) const
{
    static doublereal af_coeff[3] = { 3.666666E1, -0.1504956E-9, 0.5107997E-13};
    doublereal TC = temp - 273.15;
    doublereal presBar = pres / 1.0E5;

    if (TC < 155.0) {
        return 0.0;
    }
    TC = std::min(TC, 355.0);
    if (presBar > 1000.) {
        return 0.0;
    }


    doublereal T1 = (TC-155.0)/300.;
    doublereal p2 = (1000. - presBar) * (1000. - presBar);
    doublereal p3 = (1000. - presBar) * p2;
    doublereal p4 = p2 * p2;
    doublereal fac2 = af_coeff[1] * p3 + af_coeff[2] * p4;
    if (ifunc == 0) {
        return pow(T1,4.8) + af_coeff[0] * pow(T1, 16.0) * fac2;
    } else if (ifunc == 1) {
        return (4.8 * pow(T1,3.8) + 16.0 * af_coeff[0] * pow(T1, 15.0)) / 300. * fac2;
    } else if (ifunc == 2) {
        return (4.8 * 3.8 * pow(T1,2.8) + 16.0 * 15.0 * af_coeff[0] * pow(T1, 14.0)) / (300. * 300.) * fac2;
    } else if (ifunc == 3) {
        double fac1 = pow(T1,4.8) + af_coeff[0] * pow(T1, 16.0);
        fac2 = - (3.0 * af_coeff[1] * p2 + 4.0 * af_coeff[2] * p3)/ 1.0E5;
        return fac1 * fac2;
    } else {
        throw CanteraError("HKFT_PDSS::gg", "unimplemented");
    }
}

doublereal PDSS_HKFT::g(const doublereal temp, const doublereal pres, const int ifunc) const
{
    doublereal afunc = ag(temp, 0);
    doublereal bfunc = bg(temp, 0);
    m_waterSS->setState_TP(temp, pres);
    m_densWaterSS = m_waterSS->density();
    // density in gm cm-3
    doublereal dens = m_densWaterSS * 1.0E-3;
    doublereal gval = afunc * pow((1.0-dens), bfunc);
    if (dens >= 1.0) {
        return 0.0;
    }
    if (ifunc == 0) {
        return gval;

    } else if (ifunc == 1 || ifunc == 2) {
        doublereal afuncdT = ag(temp, 1);
        doublereal bfuncdT = bg(temp, 1);
        doublereal alpha   = m_waterSS->thermalExpansionCoeff();

        doublereal fac1 = afuncdT * gval / afunc;
        doublereal fac2 = bfuncdT * gval * log(1.0 - dens);
        doublereal fac3 = gval * alpha * bfunc * dens / (1.0 - dens);

        doublereal dgdt = fac1 + fac2 + fac3;
        if (ifunc == 1) {
            return dgdt;
        }

        doublereal afuncdT2 = ag(temp, 2);
        doublereal bfuncdT2 = bg(temp, 2);

        doublereal dfac1dT = dgdt * afuncdT / afunc + afuncdT2 * gval / afunc
                             -  afuncdT * afuncdT * gval / (afunc * afunc);

        doublereal ddensdT = - alpha * dens;
        doublereal dfac2dT =  bfuncdT2 * gval * log(1.0 - dens)
                              + bfuncdT * dgdt * log(1.0 - dens)
                              - bfuncdT * gval /(1.0 - dens) * ddensdT;

        doublereal dalphadT = m_waterSS->dthermalExpansionCoeffdT();

        doublereal dfac3dT = dgdt * alpha * bfunc * dens / (1.0 - dens)
                             + gval * dalphadT * bfunc * dens / (1.0 - dens)
                             + gval * alpha * bfuncdT * dens / (1.0 - dens)
                             + gval * alpha * bfunc * ddensdT / (1.0 - dens)
                             + gval * alpha * bfunc * dens / ((1.0 - dens) * (1.0 - dens)) * ddensdT;

        return dfac1dT + dfac2dT + dfac3dT;

    } else if (ifunc == 3) {
        doublereal beta   = m_waterSS->isothermalCompressibility();

        return - bfunc * gval * dens * beta / (1.0 - dens);
    } else {
        throw CanteraError("HKFT_PDSS::g", "unimplemented");
    }
    return 0.0;
}

doublereal PDSS_HKFT::gstar(const doublereal temp, const doublereal pres, const int ifunc) const
{
    doublereal gval = g(temp, pres, ifunc);
    doublereal fval = f(temp, pres, ifunc);
    double res = gval - fval;
#ifdef DEBUG_MODE_NOT
    if (ifunc == 2) {
        double gval1  = g(temp, pres, 1);
        double fval1  = f(temp, pres, 1);
        double gval2  = g(temp + 0.001, pres, 1);
        double fval2  = f(temp + 0.001, pres, 1);
        double gvalT  = (gval2 - gval1) / 0.001;
        double fvalT  = (fval2 - fval1) / 0.001;
        if (fabs(gvalT - gval) > 1.0E-9) {
            printf("we are here\n");
        }
        if (fabs(fvalT - fval) > 1.0E-9) {
            printf("we are here\n");
        }
    }
#endif
    return res;
}

doublereal PDSS_HKFT::LookupGe(const std::string& elemName)
{
    size_t iE = m_tp->elementIndex(elemName);
    if (iE == npos) {
        throw CanteraError("PDSS_HKFT::LookupGe", "element " + elemName + " not found");
    }
    doublereal geValue = m_tp->entropyElement298(iE);
    if (geValue == ENTROPY298_UNKNOWN) {
        throw CanteraError("PDSS_HKFT::LookupGe",
                           "element " + elemName + " does not have a supplied entropy298");
    }
    return geValue * -298.15;
}

void PDSS_HKFT::convertDGFormation()
{
    /*
     * Ok let's get the element compositions and conversion factors.
     */
    doublereal totalSum = 0.0;
    for (size_t m = 0; m < m_tp->nElements(); m++) {
        double na = m_tp->nAtoms(m_spindex, m);
        if (na > 0.0) {
            totalSum += na * LookupGe(m_tp->elementName(m));
        }
    }
    // Add in the charge
    if (m_charge_j != 0.0) {
        totalSum -= m_charge_j * LookupGe("H");
    }
    // Ok, now do the calculation. Convert to joules kmol-1
    doublereal dg = m_deltaG_formation_tr_pr * 4.184 * 1.0E3;
    //! Store the result into an internal variable.
    m_Mu0_tr_pr = dg + totalSum;
}

void PDSS_HKFT::reportParams(size_t& kindex, int& type,
                             doublereal* const c,
                             doublereal& minTemp_,
                             doublereal& maxTemp_,
                             doublereal& refPressure_) const
{
    // Fill in the first part
    PDSS::reportParams(kindex, type, c, minTemp_, maxTemp_,
                       refPressure_);

    c[0] = m_deltaG_formation_tr_pr;
    c[1] = m_deltaH_formation_tr_pr;
    c[2] = m_Mu0_tr_pr;
    c[3] = m_Entrop_tr_pr;
    c[4] =  m_a1;
    c[5] =  m_a2;
    c[6] =  m_a3;
    c[7] =  m_a4;
    c[8] =  m_c1;
    c[9] =  m_c2;
    c[10] = m_omega_pr_tr;
}

}