7da738d238
Applied using: astyle -n --style=kr --add-brackets --indent=spaces=4 --indent-col1-comments --unpad-paren --pad-header --align-pointer=type --lineend=linux
407 lines
10 KiB
C++
407 lines
10 KiB
C++
/**
|
|
* @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
|
|
{
|
|
return new GibbsExcessVPSSTP(*this);
|
|
}
|
|
|
|
/*
|
|
* -------------- 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()
|
|
{
|
|
vector_fp vbar = getPartialMolarVolumes();
|
|
// double *vbar = &m_pp[0];
|
|
// getPartialMolarVolumes(&vbar[0]);
|
|
|
|
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);
|
|
}
|
|
|
|
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);
|
|
}
|
|
|
|
const vector_fp& GibbsExcessVPSSTP::getPartialMolarVolumes() const
|
|
{
|
|
return getStandardVolumes();
|
|
}
|
|
|
|
|
|
doublereal GibbsExcessVPSSTP::err(const 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);
|
|
}
|
|
|
|
|
|
}
|
|
|