cantera/src/thermo/MargulesVPSSTP.cpp

642 lines
21 KiB
C++

/**
* @file MargulesVPSSTP.cpp
* Definitions for ThermoPhase object for phases which
* employ excess Gibbs free energy formulations related to Margules
* expansions (see \ref thermoprops
* and class \link Cantera::MargulesVPSSTP MargulesVPSSTP\endlink).
*/
/*
* 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/MargulesVPSSTP.h"
#include "cantera/thermo/ThermoFactory.h"
#include "cantera/base/stringUtils.h"
#include "cantera/base/ctml.h"
using namespace std;
namespace Cantera
{
MargulesVPSSTP::MargulesVPSSTP() :
numBinaryInteractions_(0),
formMargules_(0),
formTempModel_(0)
{
}
MargulesVPSSTP::MargulesVPSSTP(const std::string& inputFile, const std::string& id_) :
numBinaryInteractions_(0),
formMargules_(0),
formTempModel_(0)
{
initThermoFile(inputFile, id_);
}
MargulesVPSSTP::MargulesVPSSTP(XML_Node& phaseRoot, const std::string& id_) :
numBinaryInteractions_(0),
formMargules_(0),
formTempModel_(0)
{
importPhase(phaseRoot, this);
}
MargulesVPSSTP::MargulesVPSSTP(const MargulesVPSSTP& b)
{
MargulesVPSSTP::operator=(b);
}
MargulesVPSSTP& MargulesVPSSTP::operator=(const MargulesVPSSTP& b)
{
if (&b == this) {
return *this;
}
GibbsExcessVPSSTP::operator=(b);
numBinaryInteractions_ = b.numBinaryInteractions_;
m_HE_b_ij = b.m_HE_b_ij;
m_HE_c_ij = b.m_HE_c_ij;
m_HE_d_ij = b.m_HE_d_ij;
m_SE_b_ij = b.m_SE_b_ij;
m_SE_c_ij = b.m_SE_c_ij;
m_SE_d_ij = b.m_SE_d_ij;
m_VHE_b_ij = b.m_VHE_b_ij;
m_VHE_c_ij = b.m_VHE_c_ij;
m_VHE_d_ij = b.m_VHE_d_ij;
m_VSE_b_ij = b.m_VSE_b_ij;
m_VSE_c_ij = b.m_VSE_c_ij;
m_VSE_d_ij = b.m_VSE_d_ij;
m_pSpecies_A_ij = b.m_pSpecies_A_ij;
m_pSpecies_B_ij = b.m_pSpecies_B_ij;
formMargules_ = b.formMargules_;
formTempModel_ = b.formTempModel_;
return *this;
}
ThermoPhase* MargulesVPSSTP::duplMyselfAsThermoPhase() const
{
return new MargulesVPSSTP(*this);
}
// -- Activities, Standard States, Activity Concentrations -----------
void MargulesVPSSTP::getLnActivityCoefficients(doublereal* lnac) const
{
// Update the activity coefficients
s_update_lnActCoeff();
// take the exp of the internally stored coefficients.
for (size_t k = 0; k < m_kk; k++) {
lnac[k] = lnActCoeff_Scaled_[k];
}
}
// ------------ Partial Molar Properties of the Solution ------------
void MargulesVPSSTP::getChemPotentials(doublereal* mu) const
{
// First get the standard chemical potentials in molar form. This requires
// updates of standard state as a function of T and P
getStandardChemPotentials(mu);
// Update the activity coefficients
s_update_lnActCoeff();
for (size_t k = 0; k < m_kk; k++) {
double xx = std::max(moleFractions_[k], SmallNumber);
mu[k] += RT() * (log(xx) + lnActCoeff_Scaled_[k]);
}
}
doublereal MargulesVPSSTP::enthalpy_mole() const
{
size_t kk = nSpecies();
double h = 0;
vector_fp hbar(kk);
getPartialMolarEnthalpies(&hbar[0]);
for (size_t i = 0; i < kk; i++) {
h += moleFractions_[i]*hbar[i];
}
return h;
}
doublereal MargulesVPSSTP::entropy_mole() const
{
size_t kk = nSpecies();
double s = 0;
vector_fp sbar(kk);
getPartialMolarEntropies(&sbar[0]);
for (size_t i = 0; i < kk; i++) {
s += moleFractions_[i]*sbar[i];
}
return s;
}
doublereal MargulesVPSSTP::cp_mole() const
{
size_t kk = nSpecies();
double cp = 0;
vector_fp cpbar(kk);
getPartialMolarCp(&cpbar[0]);
for (size_t i = 0; i < kk; i++) {
cp += moleFractions_[i]*cpbar[i];
}
return cp;
}
doublereal MargulesVPSSTP::cv_mole() const
{
return cp_mole() - GasConstant;
}
void MargulesVPSSTP::getPartialMolarEnthalpies(doublereal* hbar) const
{
// Get the nondimensional standard state enthalpies
getEnthalpy_RT(hbar);
// dimensionalize it.
for (size_t k = 0; k < m_kk; k++) {
hbar[k] *= RT();
}
// Update the activity coefficients, This also update the internally stored
// molalities.
s_update_lnActCoeff();
s_update_dlnActCoeff_dT();
for (size_t k = 0; k < m_kk; k++) {
hbar[k] -= RT() * temperature() * dlnActCoeffdT_Scaled_[k];
}
}
void MargulesVPSSTP::getPartialMolarCp(doublereal* cpbar) const
{
// Get the nondimensional standard state entropies
getCp_R(cpbar);
double T = temperature();
// Update the activity coefficients, This also update the internally stored
// molalities.
s_update_lnActCoeff();
s_update_dlnActCoeff_dT();
for (size_t k = 0; k < m_kk; k++) {
cpbar[k] -= 2 * T * dlnActCoeffdT_Scaled_[k] + T * T * d2lnActCoeffdT2_Scaled_[k];
}
// dimensionalize it.
for (size_t k = 0; k < m_kk; k++) {
cpbar[k] *= GasConstant;
}
}
void MargulesVPSSTP::getPartialMolarEntropies(doublereal* sbar) const
{
// Get the nondimensional standard state entropies
getEntropy_R(sbar);
double T = temperature();
// Update the activity coefficients, This also update the internally stored
// molalities.
s_update_lnActCoeff();
s_update_dlnActCoeff_dT();
for (size_t k = 0; k < m_kk; k++) {
double xx = std::max(moleFractions_[k], SmallNumber);
sbar[k] += - lnActCoeff_Scaled_[k] -log(xx) - T * dlnActCoeffdT_Scaled_[k];
}
// dimensionalize it.
for (size_t k = 0; k < m_kk; k++) {
sbar[k] *= GasConstant;
}
}
void MargulesVPSSTP::getPartialMolarVolumes(doublereal* vbar) const
{
double T = temperature();
// Get the standard state values in m^3 kmol-1
getStandardVolumes(vbar);
for (size_t i = 0; i < numBinaryInteractions_; i++) {
size_t iA = m_pSpecies_A_ij[i];
size_t iB = m_pSpecies_B_ij[i];
double XA = moleFractions_[iA];
double XB = moleFractions_[iB];
double g0 = (m_VHE_b_ij[i] - T * m_VSE_b_ij[i]);
double g1 = (m_VHE_c_ij[i] - T * m_VSE_c_ij[i]);
const doublereal temp1 = g0 + g1 * XB;
const doublereal all = -1.0*XA*XB*temp1 - XA*XB*XB*g1;
for (size_t iK = 0; iK < m_kk; iK++) {
vbar[iK] += all;
}
vbar[iA] += XB * temp1;
vbar[iB] += XA * temp1 + XA*XB*g1;
}
}
void MargulesVPSSTP::initThermo()
{
initLengths();
GibbsExcessVPSSTP::initThermo();
}
void MargulesVPSSTP::initLengths()
{
dlnActCoeffdlnN_.resize(m_kk, m_kk);
}
void MargulesVPSSTP::initThermoXML(XML_Node& phaseNode, const std::string& id_)
{
if ((int) id_.size() > 0) {
string idp = phaseNode.id();
if (idp != id_) {
throw CanteraError("MargulesVPSSTP::initThermoXML", "phasenode and Id are incompatible");
}
}
// Find the Thermo XML node
if (!phaseNode.hasChild("thermo")) {
throw CanteraError("MargulesVPSSTP::initThermoXML",
"no thermo XML node");
}
XML_Node& thermoNode = phaseNode.child("thermo");
// Make sure that the thermo model is Margules
string formString = lowercase(thermoNode.attrib("model"));
if (formString != "margules") {
throw CanteraError("MargulesVPSSTP::initThermoXML",
"model name isn't Margules: " + formString);
}
// Go get all of the coefficients and factors in the activityCoefficients
// XML block
if (thermoNode.hasChild("activityCoefficients")) {
XML_Node& acNode = thermoNode.child("activityCoefficients");
string mStringa = acNode.attrib("model");
if (lowercase(mStringa) != "margules") {
throw CanteraError("MargulesVPSSTP::initThermoXML",
"Unknown activity coefficient model: " + mStringa);
}
for (size_t i = 0; i < acNode.nChildren(); i++) {
XML_Node& xmlACChild = acNode.child(i);
// Process a binary salt field, or any of the other XML fields that
// make up the Pitzer Database. Entries will be ignored if any of
// the species in the entry isn't in the solution.
if (lowercase(xmlACChild.name()) == "binaryneutralspeciesparameters") {
readXMLBinarySpecies(xmlACChild);
}
}
}
// Go down the chain
GibbsExcessVPSSTP::initThermoXML(phaseNode, id_);
}
void MargulesVPSSTP::s_update_lnActCoeff() const
{
double T = temperature();
lnActCoeff_Scaled_.assign(m_kk, 0.0);
for (size_t i = 0; i < numBinaryInteractions_; i++) {
size_t iA = m_pSpecies_A_ij[i];
size_t iB = m_pSpecies_B_ij[i];
double g0 = (m_HE_b_ij[i] - T * m_SE_b_ij[i]) / RT();
double g1 = (m_HE_c_ij[i] - T * m_SE_c_ij[i]) / RT();
double XA = moleFractions_[iA];
double XB = moleFractions_[iB];
const doublereal XAXB = XA * XB;
const doublereal g0g1XB = (g0 + g1 * XB);
const doublereal all = -1.0 * XAXB * g0g1XB - XAXB * XB * g1;
for (size_t iK = 0; iK < m_kk; iK++) {
lnActCoeff_Scaled_[iK] += all;
}
lnActCoeff_Scaled_[iA] += XB * g0g1XB;
lnActCoeff_Scaled_[iB] += XA * g0g1XB + XAXB * g1;
}
}
void MargulesVPSSTP::s_update_dlnActCoeff_dT() const
{
doublereal invT = 1.0 / temperature();
doublereal invRTT = 1.0 / GasConstant*invT*invT;
dlnActCoeffdT_Scaled_.assign(m_kk, 0.0);
d2lnActCoeffdT2_Scaled_.assign(m_kk, 0.0);
for (size_t i = 0; i < numBinaryInteractions_; i++) {
size_t iA = m_pSpecies_A_ij[i];
size_t iB = m_pSpecies_B_ij[i];
double XA = moleFractions_[iA];
double XB = moleFractions_[iB];
double g0 = -m_HE_b_ij[i] * invRTT;
double g1 = -m_HE_c_ij[i] * invRTT;
const doublereal XAXB = XA * XB;
const doublereal g0g1XB = (g0 + g1 * XB);
const doublereal all = -1.0 * XAXB * g0g1XB - XAXB * XB * g1;
const doublereal mult = 2.0 * invT;
const doublereal dT2all = mult * all;
for (size_t iK = 0; iK < m_kk; iK++) {
dlnActCoeffdT_Scaled_[iK] += all;
d2lnActCoeffdT2_Scaled_[iK] -= dT2all;
}
dlnActCoeffdT_Scaled_[iA] += XB * g0g1XB;
dlnActCoeffdT_Scaled_[iB] += XA * g0g1XB + XAXB * g1;
d2lnActCoeffdT2_Scaled_[iA] -= mult * XB * g0g1XB;
d2lnActCoeffdT2_Scaled_[iB] -= mult * (XA * g0g1XB + XAXB * g1);
}
}
void MargulesVPSSTP::getdlnActCoeffdT(doublereal* dlnActCoeffdT) const
{
s_update_dlnActCoeff_dT();
for (size_t k = 0; k < m_kk; k++) {
dlnActCoeffdT[k] = dlnActCoeffdT_Scaled_[k];
}
}
void MargulesVPSSTP::getd2lnActCoeffdT2(doublereal* d2lnActCoeffdT2) const
{
s_update_dlnActCoeff_dT();
for (size_t k = 0; k < m_kk; k++) {
d2lnActCoeffdT2[k] = d2lnActCoeffdT2_Scaled_[k];
}
}
void MargulesVPSSTP::getdlnActCoeffds(const doublereal dTds, const doublereal* const dXds,
doublereal* dlnActCoeffds) const
{
double T = temperature();
s_update_dlnActCoeff_dT();
for (size_t iK = 0; iK < m_kk; iK++) {
dlnActCoeffds[iK] = 0.0;
}
for (size_t i = 0; i < numBinaryInteractions_; i++) {
size_t iA = m_pSpecies_A_ij[i];
size_t iB = m_pSpecies_B_ij[i];
double XA = moleFractions_[iA];
double XB = moleFractions_[iB];
double dXA = dXds[iA];
double dXB = dXds[iB];
double g0 = (m_HE_b_ij[i] - T * m_SE_b_ij[i]) / RT();
double g1 = (m_HE_c_ij[i] - T * m_SE_c_ij[i]) / RT();
const doublereal g02g1XB = g0 + 2*g1*XB;
const doublereal g2XAdXB = 2*g1*XA*dXB;
const doublereal all = (-XB * dXA - XA *dXB) * g02g1XB - XB *g2XAdXB;
for (size_t iK = 0; iK < m_kk; iK++) {
dlnActCoeffds[iK] += all + dlnActCoeffdT_Scaled_[iK]*dTds;
}
dlnActCoeffds[iA] += dXB * g02g1XB;
dlnActCoeffds[iB] += dXA * g02g1XB + g2XAdXB;
}
}
void MargulesVPSSTP::s_update_dlnActCoeff_dlnN_diag() const
{
double T = temperature();
dlnActCoeffdlnN_diag_.assign(m_kk, 0.0);
for (size_t iK = 0; iK < m_kk; iK++) {
double XK = moleFractions_[iK];
for (size_t i = 0; i < numBinaryInteractions_; i++) {
size_t iA = m_pSpecies_A_ij[i];
size_t iB = m_pSpecies_B_ij[i];
size_t delAK = 0;
size_t delBK = 0;
if (iA==iK) {
delAK = 1;
} else if (iB==iK) {
delBK = 1;
}
double XA = moleFractions_[iA];
double XB = moleFractions_[iB];
double g0 = (m_HE_b_ij[i] - T * m_SE_b_ij[i]) / RT();
double g1 = (m_HE_c_ij[i] - T * m_SE_c_ij[i]) / RT();
dlnActCoeffdlnN_diag_[iK] += 2*(delBK-XB)*(g0*(delAK-XA)+g1*(2*(delAK-XA)*XB+XA*(delBK-XB)));
}
dlnActCoeffdlnN_diag_[iK] = XK*dlnActCoeffdlnN_diag_[iK];
}
}
void MargulesVPSSTP::s_update_dlnActCoeff_dlnN() const
{
double T = temperature();
dlnActCoeffdlnN_.zero();
// Loop over the activity coefficient gamma_k
for (size_t iK = 0; iK < m_kk; iK++) {
for (size_t iM = 0; iM < m_kk; iM++) {
double XM = moleFractions_[iM];
for (size_t i = 0; i < numBinaryInteractions_; i++) {
size_t iA = m_pSpecies_A_ij[i];
size_t iB = m_pSpecies_B_ij[i];
double delAK = 0.0;
double delBK = 0.0;
double delAM = 0.0;
double delBM = 0.0;
if (iA==iK) {
delAK = 1.0;
} else if (iB==iK) {
delBK = 1.0;
}
if (iA==iM) {
delAM = 1.0;
} else if (iB==iM) {
delBM = 1.0;
}
double XA = moleFractions_[iA];
double XB = moleFractions_[iB];
double g0 = (m_HE_b_ij[i] - T * m_SE_b_ij[i]) / RT();
double g1 = (m_HE_c_ij[i] - T * m_SE_c_ij[i]) / RT();
dlnActCoeffdlnN_(iK,iM) += g0*((delAM-XA)*(delBK-XB)+(delAK-XA)*(delBM-XB));
dlnActCoeffdlnN_(iK,iM) += 2*g1*((delAM-XA)*(delBK-XB)*XB+(delAK-XA)*(delBM-XB)*XB+(delBM-XB)*(delBK-XB)*XA);
}
dlnActCoeffdlnN_(iK,iM) = XM*dlnActCoeffdlnN_(iK,iM);
}
}
}
void MargulesVPSSTP::s_update_dlnActCoeff_dlnX_diag() const
{
doublereal T = temperature();
dlnActCoeffdlnX_diag_.assign(m_kk, 0.0);
for (size_t i = 0; i < numBinaryInteractions_; i++) {
size_t iA = m_pSpecies_A_ij[i];
size_t iB = m_pSpecies_B_ij[i];
doublereal XA = moleFractions_[iA];
doublereal XB = moleFractions_[iB];
doublereal g0 = (m_HE_b_ij[i] - T * m_SE_b_ij[i]) / RT();
doublereal g1 = (m_HE_c_ij[i] - T * m_SE_c_ij[i]) / RT();
dlnActCoeffdlnX_diag_[iA] += XA*XB*(2*g1*-2*g0-6*g1*XB);
dlnActCoeffdlnX_diag_[iB] += XA*XB*(2*g1*-2*g0-6*g1*XB);
}
}
void MargulesVPSSTP::getdlnActCoeffdlnN_diag(doublereal* dlnActCoeffdlnN_diag) const
{
s_update_dlnActCoeff_dlnN_diag();
for (size_t k = 0; k < m_kk; k++) {
dlnActCoeffdlnN_diag[k] = dlnActCoeffdlnN_diag_[k];
}
}
void MargulesVPSSTP::getdlnActCoeffdlnX_diag(doublereal* dlnActCoeffdlnX_diag) const
{
s_update_dlnActCoeff_dlnX_diag();
for (size_t k = 0; k < m_kk; k++) {
dlnActCoeffdlnX_diag[k] = dlnActCoeffdlnX_diag_[k];
}
}
void MargulesVPSSTP::getdlnActCoeffdlnN(const size_t ld, doublereal* dlnActCoeffdlnN)
{
s_update_dlnActCoeff_dlnN();
double* data = & dlnActCoeffdlnN_(0,0);
for (size_t k = 0; k < m_kk; k++) {
for (size_t m = 0; m < m_kk; m++) {
dlnActCoeffdlnN[ld * k + m] = data[m_kk * k + m];
}
}
}
void MargulesVPSSTP::resizeNumInteractions(const size_t num)
{
numBinaryInteractions_ = num;
m_HE_b_ij.resize(num, 0.0);
m_HE_c_ij.resize(num, 0.0);
m_HE_d_ij.resize(num, 0.0);
m_SE_b_ij.resize(num, 0.0);
m_SE_c_ij.resize(num, 0.0);
m_SE_d_ij.resize(num, 0.0);
m_VHE_b_ij.resize(num, 0.0);
m_VHE_c_ij.resize(num, 0.0);
m_VHE_d_ij.resize(num, 0.0);
m_VSE_b_ij.resize(num, 0.0);
m_VSE_c_ij.resize(num, 0.0);
m_VSE_d_ij.resize(num, 0.0);
m_pSpecies_A_ij.resize(num, npos);
m_pSpecies_B_ij.resize(num, npos);
}
void MargulesVPSSTP::readXMLBinarySpecies(XML_Node& xmLBinarySpecies)
{
string xname = xmLBinarySpecies.name();
if (xname != "binaryNeutralSpeciesParameters") {
throw CanteraError("MargulesVPSSTP::readXMLBinarySpecies",
"Incorrect name for processing this routine: " + xname);
}
vector_fp vParams;
string aName = xmLBinarySpecies.attrib("speciesA");
if (aName == "") {
throw CanteraError("MargulesVPSSTP::readXMLBinarySpecies", "no speciesA attrib");
}
string bName = xmLBinarySpecies.attrib("speciesB");
if (bName == "") {
throw CanteraError("MargulesVPSSTP::readXMLBinarySpecies", "no speciesB attrib");
}
// Find the index of the species in the current phase. It's not an error to
// not find the species. What this means is that the A-B interaction
// referred to in this block will be ignored.
size_t aSpecies = speciesIndex(aName);
if (aSpecies == npos) {
return;
}
string aspName = speciesName(aSpecies);
// @TODO Figure out what the original reason is for putting an error
// condition for charged species. Seems OK to me.
if (charge(aSpecies) != 0.0) {
throw CanteraError("MargulesVPSSTP::readXMLBinarySpecies",
"speciesA has a charge: {}", charge(aSpecies));
}
size_t bSpecies = speciesIndex(bName);
if (bSpecies == npos) {
return;
}
string bspName = speciesName(bSpecies);
if (charge(bSpecies) != 0.0) {
throw CanteraError("MargulesVPSSTP::readXMLBinarySpecies",
"speciesB has a charge: {}", charge(bSpecies));
}
resizeNumInteractions(numBinaryInteractions_ + 1);
size_t iSpot = numBinaryInteractions_ - 1;
m_pSpecies_A_ij[iSpot] = aSpecies;
m_pSpecies_B_ij[iSpot] = bSpecies;
for (size_t iChild = 0; iChild < xmLBinarySpecies.nChildren(); iChild++) {
XML_Node& xmlChild = xmLBinarySpecies.child(iChild);
string nodeName = lowercase(xmlChild.name());
// Process the binary species interaction parameters.
// They are in subblocks labeled:
// excessEnthalpy
// excessEntropy
// excessVolume_Enthalpy
// excessVolume_Entropy
// Other blocks are currently ignored.
// @TODO determine a policy about ignoring blocks that should or shouldn't be there.
if (nodeName == "excessenthalpy") {
// Get the string containing all of the values
getFloatArray(xmlChild, vParams, true, "toSI", "excessEnthalpy");
if (vParams.size() != 2) {
throw CanteraError("MargulesVPSSTP::readXMLBinarySpecies::excessEnthalpy for " + aspName
+ "::" + bspName,
"wrong number of params found. Need 2");
}
m_HE_b_ij[iSpot] = vParams[0];
m_HE_c_ij[iSpot] = vParams[1];
}
if (nodeName == "excessentropy") {
// Get the string containing all of the values
getFloatArray(xmlChild, vParams, true, "toSI", "excessEntropy");
if (vParams.size() != 2) {
throw CanteraError("MargulesVPSSTP::readXMLBinarySpecies::excessEntropy for " + aspName
+ "::" + bspName,
"wrong number of params found. Need 2");
}
m_SE_b_ij[iSpot] = vParams[0];
m_SE_c_ij[iSpot] = vParams[1];
}
if (nodeName == "excessvolume_enthalpy") {
// Get the string containing all of the values
getFloatArray(xmlChild, vParams, true, "toSI", "excessVolume_Enthalpy");
if (vParams.size() != 2) {
throw CanteraError("MargulesVPSSTP::readXMLBinarySpecies::excessVolume_Enthalpy for " + aspName
+ "::" + bspName,
"wrong number of params found. Need 2");
}
m_VHE_b_ij[iSpot] = vParams[0];
m_VHE_c_ij[iSpot] = vParams[1];
}
if (nodeName == "excessvolume_entropy") {
// Get the string containing all of the values
getFloatArray(xmlChild, vParams, true, "toSI", "excessVolume_Entropy");
if (vParams.size() != 2) {
throw CanteraError("MargulesVPSSTP::readXMLBinarySpecies::excessVolume_Entropy for " + aspName
+ "::" + bspName,
"wrong number of params found. Need 2");
}
m_VSE_b_ij[iSpot] = vParams[0];
m_VSE_c_ij[iSpot] = vParams[1];
}
}
}
}