GibbsExcessVPSSTP.cpp

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/**
 *  @file GibbsExcessVPSSTP.cpp
 *   Definitions for intermediate ThermoPhase object for phases which
 *   employ excess gibbs free energy formulations
 *  (see \ref thermoprops
 * and class \link Cantera::GibbsExcessVPSSTP GibbsExcessVPSSTP\endlink).
 *
 * Header file for a derived class of ThermoPhase that handles
 * variable pressure standard state methods for calculating
 * thermodynamic properties that are further based upon expressions
 * for the excess gibbs free energy expressed as a function of
 * the mole fractions.
 */
/*
 * Copyright (2009) 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/thermo/GibbsExcessVPSSTP.h"
#include "cantera/base/stringUtils.h"

#include <iomanip>

using namespace std;

namespace Cantera
{

/*
 * Default constructor.
 *
 */
GibbsExcessVPSSTP::GibbsExcessVPSSTP() :
    VPStandardStateTP(),
    moleFractions_(0),
    lnActCoeff_Scaled_(0),
    dlnActCoeffdT_Scaled_(0),
    d2lnActCoeffdT2_Scaled_(0),
    dlnActCoeffdlnN_diag_(0),
    dlnActCoeffdlnX_diag_(0),
    dlnActCoeffdlnN_(0,0),
    m_pp(0)
{
}

/*
 * Copy Constructor:
 *
 *  Note this stuff will not work until the underlying phase
 *  has a working copy constructor
 */
GibbsExcessVPSSTP::GibbsExcessVPSSTP(const GibbsExcessVPSSTP& b) :
    VPStandardStateTP(),
    moleFractions_(0),
    lnActCoeff_Scaled_(0),
    dlnActCoeffdT_Scaled_(0),
    d2lnActCoeffdT2_Scaled_(0),
    dlnActCoeffdlnN_diag_(0),
    dlnActCoeffdlnX_diag_(0),
    dlnActCoeffdlnN_(0,0),
    m_pp(0)
{
    GibbsExcessVPSSTP::operator=(b);
}

/*
 * operator=()
 *
 *  Note this stuff will not work until the underlying phase
 *  has a working assignment operator
 */
GibbsExcessVPSSTP& GibbsExcessVPSSTP::
operator=(const GibbsExcessVPSSTP& b)
{
    if (&b == this) {
        return *this;
    }

    VPStandardStateTP::operator=(b);

    moleFractions_       = b.moleFractions_;
    lnActCoeff_Scaled_   = b.lnActCoeff_Scaled_;
    dlnActCoeffdT_Scaled_   = b.dlnActCoeffdT_Scaled_;
    d2lnActCoeffdT2_Scaled_   = b.d2lnActCoeffdT2_Scaled_;
    dlnActCoeffdlnX_diag_ = b.dlnActCoeffdlnX_diag_;
    dlnActCoeffdlnN_diag_ = b.dlnActCoeffdlnN_diag_;
    dlnActCoeffdlnN_  = b.dlnActCoeffdlnN_;
    m_pp                 = b.m_pp;

    return *this;
}

/*
 *
 * ~GibbsExcessVPSSTP():   (virtual)
 *
 * Destructor: does nothing:
 *
 */
GibbsExcessVPSSTP::~GibbsExcessVPSSTP()
{
}

/*
 * This routine duplicates the current object and returns
 * a pointer to ThermoPhase.
 */
ThermoPhase*
GibbsExcessVPSSTP::duplMyselfAsThermoPhase() const
{
    GibbsExcessVPSSTP* mtp = new GibbsExcessVPSSTP(*this);
    return (ThermoPhase*) mtp;
}

/*
 *  -------------- Utilities -------------------------------
 */

void GibbsExcessVPSSTP::setMassFractions(const doublereal* const y)
{
    Phase::setMassFractions(y);
    getMoleFractions(DATA_PTR(moleFractions_));
}

void GibbsExcessVPSSTP::setMassFractions_NoNorm(const doublereal* const y)
{
    Phase::setMassFractions_NoNorm(y);
    getMoleFractions(DATA_PTR(moleFractions_));
}

void GibbsExcessVPSSTP::setMoleFractions(const doublereal* const x)
{
    Phase::setMoleFractions(x);
    getMoleFractions(DATA_PTR(moleFractions_));
}

void GibbsExcessVPSSTP::setMoleFractions_NoNorm(const doublereal* const x)
{
    Phase::setMoleFractions_NoNorm(x);
    getMoleFractions(DATA_PTR(moleFractions_));
}


void GibbsExcessVPSSTP::setConcentrations(const doublereal* const c)
{
    Phase::setConcentrations(c);
    getMoleFractions(DATA_PTR(moleFractions_));
}


// Equation of state type flag.
/*
 * The ThermoPhase base class returns
 * zero. Subclasses should define this to return a unique
 * non-zero value. Known constants defined for this purpose are
 * listed in mix_defs.h. The GibbsExcessVPSSTP class also returns
 * zero, as it is a non-complete class.
 */
int GibbsExcessVPSSTP::eosType() const
{
    return 0;
}



/*
 * ------------ Molar Thermodynamic Properties ----------------------
 */

/*
 *
 * ------------ Mechanical Properties ------------------------------
 *
 */

/*
 * Set the pressure at constant temperature. Units: Pa.
 * This method sets a constant within the object.
 * The mass density is not a function of pressure.
 */
void GibbsExcessVPSSTP::setPressure(doublereal p)
{
    setState_TP(temperature(), p);
}

void GibbsExcessVPSSTP::calcDensity()
{
    doublereal* vbar = NULL;
    vbar = new doublereal[m_kk];
    //    double *vbar = &m_pp[0];
    getPartialMolarVolumes(vbar);

    doublereal vtotal = 0.0;
    for (size_t i = 0; i < m_kk; i++) {
        vtotal += vbar[i] * moleFractions_[i];
    }
    doublereal dd = meanMolecularWeight() / vtotal;
    Phase::setDensity(dd);
    delete [] vbar;
}

void GibbsExcessVPSSTP::setState_TP(doublereal t, doublereal p)
{
    Phase::setTemperature(t);
    /*
     * Store the current pressure
     */
    m_Pcurrent = p;
    /*
     * update the standard state thermo
     * -> This involves calling the water function and setting the pressure
     */
    updateStandardStateThermo();

    /*
     * Calculate the partial molar volumes, and then the density of the fluid
     */
    calcDensity();
}



/*
 * - Activities, Standard States, Activity Concentrations -----------
 */
void GibbsExcessVPSSTP::getActivityConcentrations(doublereal* c) const
{
    getActivities(c);
}


doublereal GibbsExcessVPSSTP::standardConcentration(size_t k) const
{
    return 1.0;
}

doublereal GibbsExcessVPSSTP::logStandardConc(size_t k) const
{
    return 0.0;
}

void GibbsExcessVPSSTP::getActivities(doublereal* ac) const
{
    getActivityCoefficients(ac);
    getMoleFractions(DATA_PTR(moleFractions_));
    for (size_t k = 0; k < m_kk; k++) {
        ac[k] *= moleFractions_[k];
    }
}

void GibbsExcessVPSSTP::getActivityCoefficients(doublereal* const ac) const
{

    getLnActivityCoefficients(ac);

    // Protect against roundoff when taking exponentials
    for (size_t k = 0; k < m_kk; k++) {
        if (ac[k] > 700.) {
            ac[k] = exp(700.0);
        } else if (ac[k] < -700.) {
            ac[k] = exp(-700.0);
        } else {
            ac[k] = exp(ac[k]);
        }
    }
}
//====================================================================================================================

void GibbsExcessVPSSTP::getElectrochemPotentials(doublereal* mu) const
{
    getChemPotentials(mu);
    double ve = Faraday * electricPotential();
    for (size_t k = 0; k < m_kk; k++) {
        mu[k] += ve*charge(k);
    }
}

/*
 * ------------ Partial Molar Properties of the Solution ------------
 */

// Return an array of partial molar volumes for the
// species in the mixture. Units: m^3/kmol.
/*
 *  Frequently, for this class of thermodynamics representations,
 *  the excess Volume due to mixing is zero. Here, we set it as
 *  a default. It may be overridden in derived classes.
 *
 *  @param vbar   Output vector of species partial molar volumes.
 *                Length = m_kk. units are m^3/kmol.
 */
void GibbsExcessVPSSTP::getPartialMolarVolumes(doublereal* vbar) const
{
    /*
     * Get the standard state values in m^3 kmol-1
     */
    getStandardVolumes(vbar);
}



doublereal GibbsExcessVPSSTP::err(std::string msg) const
{
    throw CanteraError("GibbsExcessVPSSTP","Base class method "
                       +msg+" called. Equation of state type: "+int2str(eosType()));
    return 0;
}



double GibbsExcessVPSSTP::checkMFSum(const doublereal* const x) const
{
    doublereal norm = accumulate(x, x + m_kk, 0.0);
    if (fabs(norm - 1.0) > 1.0E-9) {
        throw CanteraError("GibbsExcessVPSSTP::checkMFSum",
                           "(MF sum - 1) exceeded tolerance of 1.0E-9:" + fp2str(norm));
    }
    return norm;
}

/*
 * Returns the units of the standard and general concentrations
 * Note they have the same units, as their divisor is
 * defined to be equal to the activity of the kth species
 * in the solution, which is unitless.
 *
 * This routine is used in print out applications where the
 * units are needed. Usually, MKS units are assumed throughout
 * the program and in the XML input files.
 *
 * On return uA contains the powers of the units (MKS assumed)
 * of the standard concentrations and generalized concentrations
 * for the kth species.
 *
 *  uA[0] = kmol units - default  = 1
 *  uA[1] = m    units - default  = -nDim(), the number of spatial
 *                                dimensions in the Phase class.
 *  uA[2] = kg   units - default  = 0;
 *  uA[3] = Pa(pressure) units - default = 0;
 *  uA[4] = Temperature units - default = 0;
 *  uA[5] = time units - default = 0
 */
void GibbsExcessVPSSTP::getUnitsStandardConc(double* uA, int k, int sizeUA) const
{
    for (int i = 0; i < sizeUA; i++) {
        if (i == 0) {
            uA[0] = 0.0;
        }
        if (i == 1) {
            uA[1] = 0.0;
        }
        if (i == 2) {
            uA[2] = 0.0;
        }
        if (i == 3) {
            uA[3] = 0.0;
        }
        if (i == 4) {
            uA[4] = 0.0;
        }
        if (i == 5) {
            uA[5] = 0.0;
        }
    }
}


/*
 * @internal Initialize. This method is provided to allow
 * subclasses to perform any initialization required after all
 * species have been added. For example, it might be used to
 * resize internal work arrays that must have an entry for
 * each species.  The base class implementation does nothing,
 * and subclasses that do not require initialization do not
 * need to overload this method.  When importing a CTML phase
 * description, this method is called just prior to returning
 * from function importPhase.
 *
 * @see importCTML.cpp
 */
void GibbsExcessVPSSTP::initThermo()
{
    initLengths();
    VPStandardStateTP::initThermo();
    getMoleFractions(DATA_PTR(moleFractions_));
}


//   Initialize lengths of local variables after all species have
//   been identified.
void  GibbsExcessVPSSTP::initLengths()
{
    m_kk = nSpecies();
    moleFractions_.resize(m_kk);
    lnActCoeff_Scaled_.resize(m_kk);
    dlnActCoeffdT_Scaled_.resize(m_kk);
    d2lnActCoeffdT2_Scaled_.resize(m_kk);
    dlnActCoeffdlnX_diag_.resize(m_kk);
    dlnActCoeffdlnN_diag_.resize(m_kk);
    dlnActCoeffdlnN_.resize(m_kk, m_kk);
    m_pp.resize(m_kk);
}


}