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cantera/Cantera/src/thermo/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.
*/
/*
* Copywrite (2009) Sandia Corporation. Under the terms of
* Contract DE-AC04-94AL85000 with Sandia Corporation, the
* U.S. Government retains certain rights in this software.
*/
/*
* $Date$
* $Revision$
*/
#include "GibbsExcessVPSSTP.h"
#include <iomanip>
using namespace std;
namespace Cantera {
/*
* Default constructor.
*
*/
GibbsExcessVPSSTP::GibbsExcessVPSSTP() :
VPStandardStateTP()
{
}
/*
* Copy Constructor:
*
* Note this stuff will not work until the underlying phase
* has a working copy constructor
*/
GibbsExcessVPSSTP::GibbsExcessVPSSTP(const GibbsExcessVPSSTP &b) :
VPStandardStateTP()
{
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_;
dlnActCoeffdlnX_Scaled_ = b.dlnActCoeffdlnX_Scaled_;
dlnActCoeffdlnN_Scaled_ = b.dlnActCoeffdlnN_Scaled_;
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) {
State::setMassFractions(y);
getMoleFractions(DATA_PTR(moleFractions_));
}
void GibbsExcessVPSSTP::setMassFractions_NoNorm(const doublereal* const y) {
State::setMassFractions_NoNorm(y);
getMoleFractions(DATA_PTR(moleFractions_));
}
void GibbsExcessVPSSTP::setMoleFractions(const doublereal* const x) {
State::setMoleFractions(x);
getMoleFractions(DATA_PTR(moleFractions_));
}
void GibbsExcessVPSSTP::setMoleFractions_NoNorm(const doublereal* const x) {
State::setMoleFractions_NoNorm(x);
getMoleFractions(DATA_PTR(moleFractions_));
}
void GibbsExcessVPSSTP::setConcentrations(const doublereal* const c) {
State::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 (int i = 0; i < m_kk; i++) {
vtotal += vbar[i] * moleFractions_[i];
}
doublereal dd = meanMolecularWeight() / vtotal;
State::setDensity(dd);
delete [] vbar;
}
void GibbsExcessVPSSTP::setState_TP(doublereal t, doublereal p) {
State::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 -----------
*/
doublereal GibbsExcessVPSSTP::standardConcentration(int k) const {
err("standardConcentration");
return -1.0;
}
doublereal GibbsExcessVPSSTP::logStandardConc(int k) const {
err("logStandardConc");
return -1.0;
}
void GibbsExcessVPSSTP::getActivities(doublereal* ac) const {
getActivityCoefficients(ac);
getMoleFractions(DATA_PTR(moleFractions_));
for (int k = 0; k < m_kk; k++) {
ac[k] *= moleFractions_[k];
}
}
void GibbsExcessVPSSTP::getElectrochemPotentials(doublereal* mu) const {
getChemPotentials(mu);
double ve = Faraday * electricPotential();
for (int 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 overriden in derived classes.
*
* @param vbar Output vector of speciar 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] = 1.0;
if (i == 1) uA[1] = -nDim();
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();
}
// 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);
dlnActCoeffdlnX_Scaled_.resize(m_kk);
dlnActCoeffdlnN_Scaled_.resize(m_kk);
m_pp.resize(m_kk);
}
/*
* Format a summary of the mixture state for output.
*/
std::string GibbsExcessVPSSTP::report(bool show_thermo) const {
char p[800];
string s = "";
try {
if (name() != "") {
sprintf(p, " \n %s:\n", name().c_str());
s += p;
}
sprintf(p, " \n temperature %12.6g K\n", temperature());
s += p;
sprintf(p, " pressure %12.6g Pa\n", pressure());
s += p;
sprintf(p, " density %12.6g kg/m^3\n", density());
s += p;
sprintf(p, " mean mol. weight %12.6g amu\n", meanMolecularWeight());
s += p;
doublereal phi = electricPotential();
sprintf(p, " potential %12.6g V\n", phi);
s += p;
int kk = nSpecies();
array_fp x(kk);
array_fp molal(kk);
array_fp mu(kk);
array_fp muss(kk);
array_fp acMolal(kk);
array_fp actMolal(kk);
getMoleFractions(&x[0]);
getChemPotentials(&mu[0]);
getStandardChemPotentials(&muss[0]);
getActivities(&actMolal[0]);
if (show_thermo) {
sprintf(p, " \n");
s += p;
sprintf(p, " 1 kg 1 kmol\n");
s += p;
sprintf(p, " ----------- ------------\n");
s += p;
sprintf(p, " enthalpy %12.6g %12.4g J\n",
enthalpy_mass(), enthalpy_mole());
s += p;
sprintf(p, " internal energy %12.6g %12.4g J\n",
intEnergy_mass(), intEnergy_mole());
s += p;
sprintf(p, " entropy %12.6g %12.4g J/K\n",
entropy_mass(), entropy_mole());
s += p;
sprintf(p, " Gibbs function %12.6g %12.4g J\n",
gibbs_mass(), gibbs_mole());
s += p;
sprintf(p, " heat capacity c_p %12.6g %12.4g J/K\n",
cp_mass(), cp_mole());
s += p;
try {
sprintf(p, " heat capacity c_v %12.6g %12.4g J/K\n",
cv_mass(), cv_mole());
s += p;
}
catch(CanteraError) {
sprintf(p, " heat capacity c_v <not implemented> \n");
s += p;
}
}
} catch (CanteraError) {
;
}
return s;
}
/*
* Format a summary of the mixture state for output.
*/
void GibbsExcessVPSSTP::reportCSV(std::ofstream& textFile, std::ofstream& csvFile, bool show_thermo) const {
csvFile.precision(6);
int tabS = 20;
int tabM = 30;
int tabL = 40;
try {
if (name() != "") {
textFile << "\n"+name()+"\n\n";
csvFile << "\n\n\n";
}
textFile << setw(tabM) << "temperature (K)\n";
csvFile << setw(tabM) << temperature() << ",\n";
textFile << setw(tabM) << "pressure (Pa)\n";
csvFile << setw(tabM) << pressure() << ",\n";
textFile << setw(tabM) << "density (kg/m^3)\n";
csvFile << setw(tabM) << density() << ",\n";
textFile << setw(tabM) << "mean mol. weight (amu)\n";
csvFile << setw(tabM) << meanMolecularWeight() << ",\n";
textFile << setw(tabM) << "potential (V)\n";
csvFile << setw(tabM) << electricPotential() << ",\n";
if (show_thermo) {
textFile << endl;
csvFile << endl;
textFile << setw(tabM) << "enthalpy (J/kg)" << "," << setw(tabM) << "enthalpy (J/kmol)\n";
csvFile << setw(tabM) << enthalpy_mass() << "," << setw(tabM) << enthalpy_mole() << ",\n";
textFile << setw(tabM) << "internal E (J/kg)" << "," << setw(tabM) << "internal E (J/kmol)\n";
csvFile << setw(tabM) << intEnergy_mass() << "," << setw(tabM) << intEnergy_mole() << ",\n";
textFile << setw(tabM) << "entropy (J/kg)" << "," << setw(tabM) << "entropy (J/kmol)\n";
csvFile << setw(tabM) << entropy_mass() << "," << setw(tabM) << entropy_mole() << ",\n";
textFile << setw(tabM) << "Gibbs (J/kg)" << "," << setw(tabM) << "Gibbs (J/kmol)\n";
csvFile << setw(tabM) << gibbs_mass() << "," << setw(tabM) << gibbs_mole() << ",\n";
textFile << setw(tabL) << "heat capacity c_p (J/K/kg)" << "," << setw(tabL) << "heat capacity c_p (J/K/kmol)\n";
csvFile << setw(tabL) << cp_mass() << "," << setw(tabL) << cp_mole() << ",\n";
textFile << setw(tabL) << "heat capacity c_v (J/K/kg)" << "," << setw(tabL) << "heat capacity c_v (J/K/kmol)\n";
csvFile << setw(tabL) << cv_mass() << "," << setw(tabL) << cv_mole() << ",\n";
}
/*
// NOT USED!!!!!
int kk = nSpecies();
array_fp x(kk);
array_fp y(kk);
array_fp mu(kk);
getMoleFractions(&x[0]);
getMassFractions(&y[0]);
getChemPotentials(&mu[0]);
doublereal rt = GasConstant * temperature();
int k;
// ThermoPhase original above...changed to below comments in GibbsExcessVPSSTP::report()
// int kk = nSpecies();
// array_fp x(kk);
// array_fp molal(kk);
// array_fp mu(kk);
// array_fp muss(kk);
// array_fp acMolal(kk);
// array_fp actMolal(kk);
// getMoleFractions(&x[0]);
//
// getChemPotentials(&mu[0]);
// getStandardChemPotentials(&muss[0]);
// getActivities(&actMolal[0]);
if (show_thermo) {
textFile << "\n" << setw(40) << "X" << "," << setw(tabS) << "Y" << "," << setw(tabS) << "Chem. Pot. / RT\n";
csvFile << "\n\n";
for (k = 0; k < kk; k++) {
if (x[k] > SmallNumber) {
textFile << setw(tabS) << speciesName(k) << ",\n";
csvFile << setw(40) << x[k] << "," << setw(tabS) << y[k] << "," << setw(tabS) << mu[k]/rt << ",\n";
}
else {
textFile << setw(tabS) << speciesName(k) << ",\n";
csvFile << setw(40) << x[k] << "," << setw(tabS) << y[k] << ",\n";
}
}
}
else {
textFile << "\n" << setw(40) << "X" << "," << setw(tabS) << "Y\n";
csvFile << "\n\n";
for (k = 0; k < kk; k++) {
textFile << setw(tabS) << speciesName(k) << ",\n";
csvFile << setw(40) << x[k] << "," << setw(tabS) << y[k] << ",\n";
}
}
*/
}
catch (CanteraError) {
;
}
}
}
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