002c158761
Move includes from header to implementation files where possible, and remove unnecessary includes.
347 lines
11 KiB
C++
347 lines
11 KiB
C++
/**
|
|
* @file MaskellSolidSolnPhase.cpp Implementation file for an ideal solid
|
|
* solution model with incompressible thermodynamics (see \ref
|
|
* thermoprops and \link Cantera::MaskellSolidSolnPhase
|
|
* MaskellSolidSolnPhase\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/thermo/MaskellSolidSolnPhase.h"
|
|
#include "cantera/base/stringUtils.h"
|
|
#include "cantera/base/xml.h"
|
|
|
|
#include <cassert>
|
|
|
|
namespace Cantera
|
|
{
|
|
//=====================================================================================================
|
|
MaskellSolidSolnPhase::MaskellSolidSolnPhase() :
|
|
m_Pref(OneAtm),
|
|
m_Pcurrent(OneAtm),
|
|
m_h0_RT(2),
|
|
m_cp0_R(2),
|
|
m_g0_RT(2),
|
|
m_s0_R(2),
|
|
h_mixing(0.0),
|
|
product_species_index(0),
|
|
reactant_species_index(1)
|
|
{
|
|
}
|
|
//=====================================================================================================
|
|
MaskellSolidSolnPhase::MaskellSolidSolnPhase(const MaskellSolidSolnPhase& b) :
|
|
m_Pref(OneAtm),
|
|
m_Pcurrent(OneAtm),
|
|
m_h0_RT(2),
|
|
m_cp0_R(2),
|
|
m_g0_RT(2),
|
|
m_s0_R(2),
|
|
h_mixing(0.0),
|
|
product_species_index(0),
|
|
reactant_species_index(1)
|
|
{
|
|
*this = b;
|
|
}
|
|
//=====================================================================================================
|
|
MaskellSolidSolnPhase&
|
|
MaskellSolidSolnPhase::operator=(const MaskellSolidSolnPhase& b)
|
|
{
|
|
if (this != &b) {
|
|
VPStandardStateTP::operator=(b);
|
|
}
|
|
return *this;
|
|
}
|
|
//=====================================================================================================
|
|
ThermoPhase* MaskellSolidSolnPhase::duplMyselfAsThermoPhase() const
|
|
{
|
|
return new MaskellSolidSolnPhase(*this);
|
|
}
|
|
//=====================================================================================================
|
|
void MaskellSolidSolnPhase::getActivityConcentrations(doublereal* c) const
|
|
{
|
|
getActivityCoefficients(c);
|
|
for(unsigned sp=0; sp < m_kk; ++sp)
|
|
{
|
|
c[sp] *= moleFraction(sp);
|
|
}
|
|
}
|
|
|
|
/********************************************************************
|
|
* Molar Thermodynamic Properties of the Solution
|
|
********************************************************************/
|
|
//=====================================================================================================
|
|
doublereal MaskellSolidSolnPhase::enthalpy_mole() const
|
|
{
|
|
_updateThermo();
|
|
const doublereal h0 = GasConstant * temperature() * mean_X(&m_h0_RT[0]);
|
|
const doublereal r = moleFraction(product_species_index);
|
|
const doublereal fmval = fm(r);
|
|
return h0 + r * fmval * h_mixing;
|
|
}
|
|
//=====================================================================================================
|
|
doublereal xlogx(doublereal x)
|
|
{
|
|
return x * std::log(x);
|
|
}
|
|
|
|
doublereal MaskellSolidSolnPhase::entropy_mole() const
|
|
{
|
|
_updateThermo();
|
|
const doublereal s0 = GasConstant * mean_X(&m_s0_R[0]);
|
|
const doublereal r = moleFraction(product_species_index);
|
|
const doublereal fmval = fm(r);
|
|
const doublereal rfm = r * fmval;
|
|
return s0 + GasConstant * (xlogx(1-rfm) - xlogx(rfm) - xlogx(1-r-rfm) - xlogx((1-fmval)*r) - xlogx(1-r) - xlogx(r));
|
|
}
|
|
|
|
/********************************************************************
|
|
* Mechanical Equation of State
|
|
********************************************************************/
|
|
|
|
void MaskellSolidSolnPhase::setDensity(const doublereal rho)
|
|
{
|
|
/*
|
|
* Unless the input density is exactly equal to the density
|
|
* calculated and stored in the State object, we throw an
|
|
* exception. This is because the density is NOT an
|
|
* independent variable.
|
|
*/
|
|
double dens = density();
|
|
if (rho != dens) {
|
|
throw CanteraError("MaskellSolidSolnPhase::setDensity",
|
|
"Density is not an independent variable");
|
|
}
|
|
}
|
|
|
|
void MaskellSolidSolnPhase::calcDensity()
|
|
{
|
|
const vector_fp & vbar = getStandardVolumes();
|
|
|
|
vector_fp moleFracs(m_kk);
|
|
Phase::getMoleFractions(&moleFracs[0]);
|
|
doublereal vtotal = 0.0;
|
|
for (size_t i = 0; i < m_kk; i++) {
|
|
vtotal += vbar[i] * moleFracs[i];
|
|
}
|
|
doublereal dd = meanMolecularWeight() / vtotal;
|
|
Phase::setDensity(dd);
|
|
}
|
|
|
|
void MaskellSolidSolnPhase::setPressure(doublereal p)
|
|
{
|
|
m_Pcurrent = p;
|
|
}
|
|
|
|
void MaskellSolidSolnPhase::setMolarDensity(const doublereal n)
|
|
{
|
|
throw CanteraError("MaskellSolidSolnPhase::setMolarDensity",
|
|
"Density is not an independent variable");
|
|
}
|
|
|
|
/********************************************************************
|
|
* Chemical Potentials and Activities
|
|
********************************************************************/
|
|
|
|
void MaskellSolidSolnPhase::getActivityCoefficients(doublereal* ac) const
|
|
{
|
|
_updateThermo();
|
|
static const int cacheId = m_cache.getId();
|
|
CachedArray cached = m_cache.getArray(cacheId);
|
|
if( !cached.validate(temperature(), pressure(), stateMFNumber()) ) {
|
|
cached.value.resize(2);
|
|
|
|
const doublereal r = moleFraction(product_species_index);
|
|
const doublereal pval = p(r);
|
|
const doublereal fmval = fm(r);
|
|
const doublereal rfm = r * fmval;
|
|
const doublereal RT = GasConstant * temperature();
|
|
const doublereal A = (std::pow(1 - rfm, pval) * std::pow(rfm, pval) * std::pow(r - rfm, 1 - pval)) /
|
|
(std::pow(1 - r - rfm, 1 + pval) * (1 - r));
|
|
const doublereal B = pval * h_mixing / RT;
|
|
cached.value[product_species_index] = A * std::exp(B);
|
|
cached.value[reactant_species_index] = 1 / (A * r * (1-r) ) * std::exp(-B);
|
|
}
|
|
std::copy(cached.value.begin(), cached.value.end(), ac);
|
|
}
|
|
|
|
void MaskellSolidSolnPhase::getChemPotentials(doublereal* mu) const
|
|
{
|
|
_updateThermo();
|
|
const doublereal r = moleFraction(product_species_index);
|
|
const doublereal pval = p(r);
|
|
const doublereal fmval = fm(r);
|
|
const doublereal rfm = r * fmval;
|
|
const doublereal RT = GasConstant * temperature();
|
|
const doublereal DgbarDr = pval * h_mixing +
|
|
GasConstant * temperature() *
|
|
std::log( (std::pow(1 - rfm, pval) * std::pow(rfm, pval) * std::pow(r - rfm, 1 - pval) * r) /
|
|
(std::pow(1 - r - rfm, 1 + pval) * (1 - r)) );
|
|
mu[product_species_index] = RT * m_g0_RT[product_species_index] + DgbarDr;
|
|
mu[reactant_species_index] = RT * m_g0_RT[reactant_species_index] - DgbarDr;
|
|
}
|
|
|
|
void MaskellSolidSolnPhase::getChemPotentials_RT(doublereal* mu) const
|
|
{
|
|
const doublereal invRT = 1.0 / (GasConstant * temperature());
|
|
getChemPotentials(mu);
|
|
for(unsigned sp=0; sp < m_kk; ++sp)
|
|
{
|
|
mu[sp] *= invRT;
|
|
}
|
|
}
|
|
|
|
/********************************************************************
|
|
* Partial Molar Properties
|
|
********************************************************************/
|
|
|
|
void MaskellSolidSolnPhase::getPartialMolarEnthalpies(doublereal* hbar) const
|
|
{
|
|
throw CanteraError("MaskellSolidSolnPhase::getPartialMolarEnthalpies()", "Not yet implemented.");
|
|
}
|
|
|
|
void MaskellSolidSolnPhase::getPartialMolarEntropies(doublereal* sbar) const
|
|
{
|
|
throw CanteraError("MaskellSolidSolnPhase::getPartialMolarEntropies()", "Not yet implemented.");
|
|
}
|
|
|
|
void MaskellSolidSolnPhase::getPartialMolarCp(doublereal* cpbar) const
|
|
{
|
|
throw CanteraError("MaskellSolidSolnPhase::getPartialMolarCp()", "Not yet implemented.");
|
|
}
|
|
|
|
void MaskellSolidSolnPhase::getPartialMolarVolumes(doublereal* vbar) const
|
|
{
|
|
getStandardVolumes(vbar);
|
|
}
|
|
|
|
void MaskellSolidSolnPhase::getPureGibbs(doublereal* gpure) const
|
|
{
|
|
_updateThermo();
|
|
const doublereal RT = GasConstant * temperature();
|
|
for(unsigned sp=0; sp < m_kk; ++sp)
|
|
{
|
|
gpure[sp] = RT * m_g0_RT[sp];
|
|
}
|
|
}
|
|
|
|
void MaskellSolidSolnPhase::getStandardChemPotentials(doublereal* mu) const
|
|
{
|
|
// What is the difference between this and getPureGibbs? IdealSolidSolnPhase gives the same for both
|
|
getPureGibbs(mu);
|
|
}
|
|
|
|
/*********************************************************************
|
|
* Utility Functions
|
|
*********************************************************************/
|
|
void MaskellSolidSolnPhase::initThermoXML(XML_Node& phaseNode, const std::string& id_)
|
|
{
|
|
std::string subname = "MaskellSolidSolnPhase::initThermoXML";
|
|
if (id_.size() > 0) {
|
|
std::string idp = phaseNode.id();
|
|
if (idp != id_) {
|
|
throw CanteraError(subname.c_str(),
|
|
"phasenode and Id are incompatible");
|
|
}
|
|
}
|
|
|
|
/*
|
|
* Check on the thermo field. Must have:
|
|
* <thermo model="MaskellSolidSolution" />
|
|
*/
|
|
if (phaseNode.hasChild("thermo")) {
|
|
XML_Node& thNode = phaseNode.child("thermo");
|
|
std::string mStringa = thNode.attrib("model");
|
|
std::string mString = lowercase(mStringa);
|
|
if (mString != "maskellsolidsolnphase") {
|
|
throw CanteraError(subname.c_str(),
|
|
"Unknown thermo model: " + mStringa);
|
|
}
|
|
|
|
|
|
/*
|
|
* Parse the enthalpy of mixing constant
|
|
*/
|
|
if (thNode.hasChild("h_mix")) {
|
|
XML_Node& scNode = thNode.child("h_mix");
|
|
set_h_mix(fpValue(scNode.value()));
|
|
} else {
|
|
throw CanteraError(subname.c_str(),
|
|
"Mixing enthalpy parameter not specified.");
|
|
}
|
|
|
|
if (thNode.hasChild("product_species")) {
|
|
XML_Node& scNode = thNode.child("product_species");
|
|
std::string product_species_name = scNode.value();
|
|
product_species_index = speciesIndex(product_species_name);
|
|
if( product_species_index == static_cast<int>(npos) )
|
|
{
|
|
throw CanteraError(subname.c_str(),
|
|
"Species " + product_species_name + " not found.");
|
|
}
|
|
if( product_species_index == 0 )
|
|
{
|
|
reactant_species_index = 1;
|
|
} else {
|
|
reactant_species_index = 0;
|
|
}
|
|
}
|
|
|
|
} else {
|
|
throw CanteraError(subname.c_str(),
|
|
"Unspecified thermo model");
|
|
}
|
|
|
|
|
|
// Confirm that the phase only contains 2 species
|
|
if( m_kk != 2 )
|
|
{
|
|
throw CanteraError( subname.c_str(), "MaskellSolidSolution model requires exactly 2 species.");
|
|
}
|
|
|
|
/*
|
|
* Call the base initThermo, which handles setting the initial
|
|
* state.
|
|
*/
|
|
VPStandardStateTP::initThermoXML(phaseNode, id_);
|
|
}
|
|
|
|
void MaskellSolidSolnPhase::_updateThermo() const
|
|
{
|
|
assert(m_kk == 2);
|
|
static const int cacheId = m_cache.getId();
|
|
CachedScalar cached = m_cache.getScalar(cacheId);
|
|
/*
|
|
* Update the thermodynamic functions of the reference state.
|
|
*/
|
|
doublereal tnow = temperature();
|
|
if( !cached.validate(tnow) )
|
|
{
|
|
m_spthermo->update(tnow, DATA_PTR(m_cp0_R), DATA_PTR(m_h0_RT),
|
|
DATA_PTR(m_s0_R));
|
|
for (size_t k = 0; k < m_kk; k++) {
|
|
m_g0_RT[k] = m_h0_RT[k] - m_s0_R[k];
|
|
}
|
|
}
|
|
}
|
|
|
|
doublereal MaskellSolidSolnPhase::s() const
|
|
{
|
|
return 1 + std::exp(h_mixing / (GasConstant * temperature()));
|
|
}
|
|
|
|
doublereal MaskellSolidSolnPhase::fm(const doublereal r) const
|
|
{
|
|
const doublereal sval = s();
|
|
return (1 - std::sqrt(1 - 4*r*(1-r)/sval)) / (2*r);
|
|
}
|
|
|
|
doublereal MaskellSolidSolnPhase::p(const doublereal r) const
|
|
{
|
|
const doublereal sval = s();
|
|
return (1 - 2*r) / std::sqrt(sval*sval - 4 * sval * r + 4 * sval * r * r);
|
|
}
|
|
|
|
} // end namespace Cantera
|