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cantera/src/thermo/MargulesVPSSTP.cpp

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/**
* @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).
*
*/
/*
* 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.
*/
#include "cantera/thermo/MargulesVPSSTP.h"
#include "cantera/thermo/ThermoFactory.h"
#include <iomanip>
using namespace std;
namespace Cantera
{
static const double xxSmall = 1.0E-150;
/*
* Default constructor.
*
*/
MargulesVPSSTP::MargulesVPSSTP() :
GibbsExcessVPSSTP(),
numBinaryInteractions_(0),
formMargules_(0),
formTempModel_(0)
{
}
/*
* Working constructors
*
* The two constructors below are the normal way
* the phase initializes itself. They are shells that call
* the routine initThermo(), with a reference to the
* XML database to get the info for the phase.
*/
MargulesVPSSTP::MargulesVPSSTP(std::string inputFile, std::string id) :
GibbsExcessVPSSTP(),
numBinaryInteractions_(0),
formMargules_(0),
formTempModel_(0)
{
constructPhaseFile(inputFile, id);
}
MargulesVPSSTP::MargulesVPSSTP(XML_Node& phaseRoot, std::string id) :
GibbsExcessVPSSTP(),
numBinaryInteractions_(0),
formMargules_(0),
formTempModel_(0)
{
constructPhaseXML(phaseRoot, id);
}
/*
* Copy Constructor:
*
* Note this stuff will not work until the underlying phase
* has a working copy constructor
*/
MargulesVPSSTP::MargulesVPSSTP(const MargulesVPSSTP& b) :
GibbsExcessVPSSTP()
{
MargulesVPSSTP::operator=(b);
}
/*
* operator=()
*
* Note this stuff will not work until the underlying phase
* has a working assignment operator
*/
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;
}
/**
*
* ~MargulesVPSSTP(): (virtual)
*
* Destructor: does nothing:
*
*/
MargulesVPSSTP::~MargulesVPSSTP()
{
}
/*
* This routine duplicates the current object and returns
* a pointer to ThermoPhase.
*/
ThermoPhase*
MargulesVPSSTP::duplMyselfAsThermoPhase() const
{
MargulesVPSSTP* mtp = new MargulesVPSSTP(*this);
return (ThermoPhase*) mtp;
}
// Special constructor for a hard-coded problem
/*
*
* LiKCl treating the PseudoBinary layer as passthrough.
* -> test to predict the eutectic and liquidus correctly.
*
*/
MargulesVPSSTP::MargulesVPSSTP(int testProb) :
GibbsExcessVPSSTP(),
numBinaryInteractions_(0),
formMargules_(0),
formTempModel_(0)
{
constructPhaseFile("LiKCl_liquid.xml", "");
numBinaryInteractions_ = 1;
m_HE_b_ij.resize(1);
m_HE_c_ij.resize(1);
m_HE_d_ij.resize(1);
m_SE_b_ij.resize(1);
m_SE_c_ij.resize(1);
m_SE_d_ij.resize(1);
m_VHE_b_ij.resize(1);
m_VHE_c_ij.resize(1);
m_VHE_d_ij.resize(1);
m_VSE_b_ij.resize(1);
m_VSE_c_ij.resize(1);
m_VSE_d_ij.resize(1);
m_pSpecies_A_ij.resize(1);
m_pSpecies_B_ij.resize(1);
m_HE_b_ij[0] = -17570E3;
m_HE_c_ij[0] = -377.0E3;
m_HE_d_ij[0] = 0.0;
m_SE_b_ij[0] = -7.627E3;
m_SE_c_ij[0] = 4.958E3;
m_SE_d_ij[0] = 0.0;
size_t iLiCl = speciesIndex("LiCl(L)");
if (iLiCl == npos) {
throw CanteraError("MargulesVPSSTP test1 constructor",
"Unable to find LiCl(L)");
}
m_pSpecies_B_ij[0] = iLiCl;
size_t iKCl = speciesIndex("KCl(L)");
if (iKCl == npos) {
throw CanteraError("MargulesVPSSTP test1 constructor",
"Unable to find KCl(L)");
}
m_pSpecies_A_ij[0] = iKCl;
}
/*
* -------------- Utilities -------------------------------
*/
// 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 MargulesVPSSTP class also returns
* zero, as it is a non-complete class.
*/
int MargulesVPSSTP::eosType() const
{
return 0;
}
/*
* Import, construct, and initialize a phase
* specification from an XML tree into the current object.
*
* This routine is a precursor to constructPhaseXML(XML_Node*)
* routine, which does most of the work.
*
* @param infile XML file containing the description of the
* phase
*
* @param id Optional parameter identifying the name of the
* phase. If none is given, the first XML
* phase element will be used.
*/
void MargulesVPSSTP::constructPhaseFile(std::string inputFile, std::string id)
{
if ((int) inputFile.size() == 0) {
throw CanteraError("MargulesVPSSTP:constructPhaseFile",
"input file is null");
}
string path = findInputFile(inputFile);
std::ifstream fin(path.c_str());
if (!fin) {
throw CanteraError("MargulesVPSSTP:constructPhaseFile","could not open "
+path+" for reading.");
}
/*
* The phase object automatically constructs an XML object.
* Use this object to store information.
*/
XML_Node& phaseNode_XML = xml();
XML_Node* fxml = new XML_Node();
fxml->build(fin);
XML_Node* fxml_phase = findXMLPhase(fxml, id);
if (!fxml_phase) {
throw CanteraError("MargulesVPSSTP:constructPhaseFile",
"ERROR: Can not find phase named " +
id + " in file named " + inputFile);
}
fxml_phase->copy(&phaseNode_XML);
constructPhaseXML(*fxml_phase, id);
delete fxml;
}
/*
* Import, construct, and initialize a HMWSoln phase
* specification from an XML tree into the current object.
*
* Most of the work is carried out by the cantera base
* routine, importPhase(). That routine imports all of the
* species and element data, including the standard states
* of the species.
*
* Then, In this routine, we read the information
* particular to the specification of the activity
* coefficient model for the Pitzer parameterization.
*
* We also read information about the molar volumes of the
* standard states if present in the XML file.
*
* @param phaseNode This object must be the phase node of a
* complete XML tree
* description of the phase, including all of the
* species data. In other words while "phase" must
* point to an XML phase object, it must have
* sibling nodes "speciesData" that describe
* the species in the phase.
* @param id ID of the phase. If nonnull, a check is done
* to see if phaseNode is pointing to the phase
* with the correct id.
*/
void MargulesVPSSTP::constructPhaseXML(XML_Node& phaseNode, std::string id)
{
string stemp;
if ((int) id.size() > 0) {
string idp = phaseNode.id();
if (idp != id) {
throw CanteraError("MargulesVPSSTP::constructPhaseXML",
"phasenode and Id are incompatible");
}
}
/*
* Find the Thermo XML node
*/
if (!phaseNode.hasChild("thermo")) {
throw CanteraError("MargulesVPSSTP::constructPhaseXML",
"no thermo XML node");
}
XML_Node& thermoNode = phaseNode.child("thermo");
/*
* Make sure that the thermo model is Margules
*/
stemp = thermoNode.attrib("model");
string formString = lowercase(stemp);
if (formString != "margules") {
throw CanteraError("MargulesVPSSTP::constructPhaseXML",
"model name isn't Margules: " + formString);
}
/*
* Call the Cantera importPhase() function. This will import
* all of the species into the phase. This will also handle
* all of the solvent and solute standard states
*/
bool m_ok = importPhase(phaseNode, this);
if (!m_ok) {
throw CanteraError("MargulesVPSSTP::constructPhaseXML","importPhase failed ");
}
}
/*
* ------------ Molar Thermodynamic Properties ----------------------
*/
/*
* - Activities, Standard States, Activity Concentrations -----------
*/
//====================================================================================================================
// Get the array of non-dimensional molar-based ln activity coefficients at
// the current solution temperature, pressure, and solution concentration.
/*
* @param lnac Output vector of ln activity coefficients. Length: m_kk.
*/
void MargulesVPSSTP::getLnActivityCoefficients(doublereal* lnac) const
{
/*
* Update the activity coefficients
*/
s_update_lnActCoeff();
/*
* take the exp of the internally storred coefficients.
*/
for (size_t k = 0; k < m_kk; k++) {
lnac[k] = lnActCoeff_Scaled_[k];
}
}
//====================================================================================================================
/*
* ------------ Partial Molar Properties of the Solution ------------
*/
void MargulesVPSSTP::getElectrochemPotentials(doublereal* mu) const
{
getChemPotentials(mu);
double ve = Faraday * electricPotential();
for (size_t k = 0; k < m_kk; k++) {
mu[k] += ve*charge(k);
}
}
void MargulesVPSSTP::getChemPotentials(doublereal* mu) const
{
doublereal xx;
/*
* 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();
doublereal RT = GasConstant * temperature();
for (size_t k = 0; k < m_kk; k++) {
xx = std::max(moleFractions_[k], xxSmall);
mu[k] += RT * (log(xx) + lnActCoeff_Scaled_[k]);
}
}
/// Molar enthalpy. Units: J/kmol.
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;
}
/// Molar entropy. Units: J/kmol.
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;
}
/// Molar heat capacity at constant pressure. Units: J/kmol/K.
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;
}
/// Molar heat capacity at constant volume. Units: J/kmol/K.
doublereal MargulesVPSSTP::cv_mole() const
{
return cp_mole() - GasConstant;
}
// Returns an array of partial molar enthalpies for the species
// in the mixture.
/*
* Units (J/kmol)
*
* For this phase, the partial molar enthalpies are equal to the
* standard state enthalpies modified by the derivative of the
* molality-based activity coefficent wrt temperature
*
* \f[
* \bar h_k(T,P) = h^o_k(T,P) - R T^2 \frac{d \ln(\gamma_k)}{dT}
* \f]
*
*/
void MargulesVPSSTP::getPartialMolarEnthalpies(doublereal* hbar) const
{
/*
* Get the nondimensional standard state enthalpies
*/
getEnthalpy_RT(hbar);
/*
* dimensionalize it.
*/
double T = temperature();
double RT = GasConstant * T;
for (size_t k = 0; k < m_kk; k++) {
hbar[k] *= RT;
}
/*
* Update the activity coefficients, This also update the
* internally storred molalities.
*/
s_update_lnActCoeff();
s_update_dlnActCoeff_dT();
double RTT = RT * T;
for (size_t k = 0; k < m_kk; k++) {
hbar[k] -= RTT * dlnActCoeffdT_Scaled_[k];
}
}
// Returns an array of partial molar heat capacities for the species
// in the mixture.
/*
* Units (J/kmol)
*
* For this phase, the partial molar enthalpies are equal to the
* standard state enthalpies modified by the derivative of the
* activity coefficent wrt temperature
*
* \f[
* ??????????? \bar s_k(T,P) = s^o_k(T,P) - R T^2 \frac{d \ln(\gamma_k)}{dT}
* \f]
*
*/
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 storred 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;
}
}
// Returns an array of partial molar entropies for the species
// in the mixture.
/*
* Units (J/kmol)
*
* For this phase, the partial molar enthalpies are equal to the
* standard state enthalpies modified by the derivative of the
* activity coefficent wrt temperature
*
* \f[
* \bar s_k(T,P) = s^o_k(T,P) - R T^2 \frac{d \ln(\gamma_k)}{dT}
* \f]
*
*/
void MargulesVPSSTP::getPartialMolarEntropies(doublereal* sbar) const
{
double xx;
/*
* Get the nondimensional standard state entropies
*/
getEntropy_R(sbar);
double T = temperature();
/*
* Update the activity coefficients, This also update the
* internally storred molalities.
*/
s_update_lnActCoeff();
s_update_dlnActCoeff_dT();
for (size_t k = 0; k < m_kk; k++) {
xx = std::max(moleFractions_[k], xxSmall);
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;
}
}
/*
* ------------ 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 MargulesVPSSTP::getPartialMolarVolumes(doublereal* vbar) const
{
size_t iA, iB, delAK, delBK;
double XA, XB, g0 , g1;
double T = temperature();
/*
* Get the standard state values in m^3 kmol-1
*/
getStandardVolumes(vbar);
for (size_t iK = 0; iK < m_kk; iK++) {
delAK = 0;
delBK = 0;
for (size_t i = 0; i < numBinaryInteractions_; i++) {
iA = m_pSpecies_A_ij[i];
iB = m_pSpecies_B_ij[i];
if (iA==iK) {
delAK = 1;
} else if (iB==iK) {
delBK = 1;
}
XA = moleFractions_[iA];
XB = moleFractions_[iB];
g0 = (m_VHE_b_ij[i] - T * m_VSE_b_ij[i]);
g1 = (m_VHE_c_ij[i] - T * m_VSE_c_ij[i]);
vbar[iK] += XA*XB*(g0+g1*XB)+((delAK-XA)*XB+XA*(delBK-XB))*(g0+g1*XB)+XA*XB*(delBK-XB)*g1;
}
}
}
doublereal MargulesVPSSTP::err(std::string msg) const
{
throw CanteraError("MargulesVPSSTP","Base class method "
+msg+" called. Equation of state type: "+int2str(eosType()));
return 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 MargulesVPSSTP::initThermo()
{
initLengths();
GibbsExcessVPSSTP::initThermo();
}
// Initialize lengths of local variables after all species have
// been identified.
void MargulesVPSSTP::initLengths()
{
m_kk = nSpecies();
dlnActCoeffdlnN_.resize(m_kk, m_kk);
}
/*
* initThermoXML() (virtual from ThermoPhase)
* Import and initialize a ThermoPhase object
*
* @param phaseNode This object must be the phase node of a
* complete XML tree
* description of the phase, including all of the
* species data. In other words while "phase" must
* point to an XML phase object, it must have
* sibling nodes "speciesData" that describe
* the species in the phase.
* @param id ID of the phase. If nonnull, a check is done
* to see if phaseNode is pointing to the phase
* with the correct id.
*/
void MargulesVPSSTP::initThermoXML(XML_Node& phaseNode, std::string id)
{
string subname = "MargulesVPSSTP::initThermoXML";
string stemp;
/*
* Check on the thermo field. Must have:
* <thermo model="IdealSolidSolution" />
*/
XML_Node& thermoNode = phaseNode.child("thermo");
string mStringa = thermoNode.attrib("model");
string mString = lowercase(mStringa);
if (mString != "margules") {
throw CanteraError(subname.c_str(),
"Unknown thermo model: " + mStringa);
}
/*
* Go get all of the coefficients and factors in the
* activityCoefficients XML block
*/
/*
* Go get all of the coefficients and factors in the
* activityCoefficients XML block
*/
XML_Node* acNodePtr = 0;
if (thermoNode.hasChild("activityCoefficients")) {
XML_Node& acNode = thermoNode.child("activityCoefficients");
acNodePtr = &acNode;
string mStringa = acNode.attrib("model");
string mString = lowercase(mStringa);
if (mString != "margules") {
throw CanteraError(subname.c_str(),
"Unknown activity coefficient model: " + mStringa);
}
for (size_t i = 0; i < acNodePtr->nChildren(); i++) {
XML_Node& xmlACChild = acNodePtr->child(i);
stemp = xmlACChild.name();
string nodeName = lowercase(stemp);
/*
* 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 (nodeName == "binaryneutralspeciesparameters") {
readXMLBinarySpecies(xmlACChild);
}
}
}
/*
* Go down the chain
*/
GibbsExcessVPSSTP::initThermoXML(phaseNode, id);
}
//===================================================================================================================
// Update the activity coefficients
/*
* This function will be called to update the internally storred
* natural logarithm of the activity coefficients
*
* he = X_A X_B(B + C X_B)
*/
void MargulesVPSSTP::s_update_lnActCoeff() const
{
size_t iA, iB, iK, delAK, delBK;
double XA, XB, g0 , g1;
double T = temperature();
double RT = GasConstant*T;
lnActCoeff_Scaled_.assign(m_kk, 0.0);
for (iK = 0; iK < m_kk; iK++) {
for (size_t i = 0; i < numBinaryInteractions_; i++) {
iA = m_pSpecies_A_ij[i];
iB = m_pSpecies_B_ij[i];
delAK = 0;
delBK = 0;
if (iA==iK) {
delAK = 1;
} else if (iB==iK) {
delBK = 1;
}
XA = moleFractions_[iA];
XB = moleFractions_[iB];
g0 = (m_HE_b_ij[i] - T * m_SE_b_ij[i]) / RT;
g1 = (m_HE_c_ij[i] - T * m_SE_c_ij[i]) / RT;
lnActCoeff_Scaled_[iK] += (delAK * XB + XA * delBK - XA * XB) * (g0 + g1 * XB) + XA * XB * (delBK - XB) * g1;
}
}
}
//===================================================================================================================
// Update the derivative of the log of the activity coefficients wrt T
/*
* This function will be called to update the internally storred
* natural logarithm of the activity coefficients
*
* he = X_A X_B(B + C X_B)
*/
void MargulesVPSSTP::s_update_dlnActCoeff_dT() const
{
size_t iA, iB, iK, delAK, delBK;
doublereal XA, XB, g0, g1;
doublereal T = temperature();
doublereal RTT = GasConstant*T*T;
dlnActCoeffdT_Scaled_.assign(m_kk, 0.0);
d2lnActCoeffdT2_Scaled_.assign(m_kk, 0.0);
for (iK = 0; iK < m_kk; iK++) {
for (size_t i = 0; i < numBinaryInteractions_; i++) {
iA = m_pSpecies_A_ij[i];
iB = m_pSpecies_B_ij[i];
delAK = 0;
delBK = 0;
if (iA==iK) {
delAK = 1;
} else if (iB==iK) {
delBK = 1;
}
XA = moleFractions_[iA];
XB = moleFractions_[iB];
g0 = -m_HE_b_ij[i] / RTT;
g1 = -m_HE_c_ij[i] / RTT;
double temp = (delAK * XB + XA * delBK - XA * XB) * (g0 + g1 * XB) + XA * XB * (delBK - XB) * g1;
dlnActCoeffdT_Scaled_[iK] += temp;
d2lnActCoeffdT2_Scaled_[iK] -= 2.0 * temp / T;
}
}
}
//====================================================================================================================
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];
}
}
//====================================================================================================================
// Get the change in activity coefficients w.r.t. change in state (temp, mole fraction, etc.) along
// a line in parameter space or along a line in physical space
/*
*
* @param dTds Input of temperature change along the path
* @param dXds Input vector of changes in mole fraction along the path. length = m_kk
* Along the path length it must be the case that the mole fractions sum to one.
* @param dlnActCoeffds Output vector of the directional derivatives of the
* log Activity Coefficients along the path. length = m_kk
* units are 1/units(s). if s is a physical coordinate then the units are 1/m.
*/
void MargulesVPSSTP::getdlnActCoeffds(const doublereal dTds, const doublereal* const dXds,
doublereal* dlnActCoeffds) const
{
size_t iA, iB, iK, delAK, delBK;
double XA, XB, g0 , g1, dXA, dXB;
double T = temperature();
double RT = GasConstant*T;
//fvo_zero_dbl_1(dlnActCoeff, m_kk);
s_update_dlnActCoeff_dT();
for (iK = 0; iK < m_kk; iK++) {
dlnActCoeffds[iK] = 0.0;
for (size_t i = 0; i < numBinaryInteractions_; i++) {
iA = m_pSpecies_A_ij[i];
iB = m_pSpecies_B_ij[i];
delAK = 0;
delBK = 0;
if (iA==iK) {
delAK = 1;
} else if (iB==iK) {
delBK = 1;
}
XA = moleFractions_[iA];
XB = moleFractions_[iB];
dXA = dXds[iA];
dXB = dXds[iB];
g0 = (m_HE_b_ij[i] - T * m_SE_b_ij[i]) / RT;
g1 = (m_HE_c_ij[i] - T * m_SE_c_ij[i]) / RT;
dlnActCoeffds[iK] += ((delBK-XB)*dXA + (delAK-XA)*dXB)*(g0+2*g1*XB) + (delBK-XB)*2*g1*XA*dXB
+ dlnActCoeffdT_Scaled_[iK]*dTds;
}
}
}
//====================================================================================================================
// Update the derivative of the log of the activity coefficients wrt dlnN
/*
* This function will be called to update the internally stored gradients of the
* logarithm of the activity coefficients. These are used in the determination
* of the diffusion coefficients.
*
* he = X_A X_B(B + C X_B)
*/
void MargulesVPSSTP::s_update_dlnActCoeff_dlnN_diag() const
{
size_t iA, iB, iK, delAK, delBK;
double XA, XB, XK, g0 , g1;
double T = temperature();
double RT = GasConstant*T;
dlnActCoeffdlnN_diag_.assign(m_kk, 0.0);
for (iK = 0; iK < m_kk; iK++) {
XK = moleFractions_[iK];
for (size_t i = 0; i < numBinaryInteractions_; i++) {
iA = m_pSpecies_A_ij[i];
iB = m_pSpecies_B_ij[i];
delAK = 0;
delBK = 0;
if (iA==iK) {
delAK = 1;
} else if (iB==iK) {
delBK = 1;
}
XA = moleFractions_[iA];
XB = moleFractions_[iB];
g0 = (m_HE_b_ij[i] - T * m_SE_b_ij[i]) / RT;
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)));
// double gfac = g0 + g1 * XB;
// double gggg = (delBK - XB) * g1;
// dlnActCoeffdlnN_diag_[iK] += gfac * delAK * ( - XB + delBK);
// dlnActCoeffdlnN_diag_[iK] += gfac * delBK * ( - XA + delAK);
// dlnActCoeffdlnN_diag_[iK] += gfac * (2.0 * XA * XB - delAK * XB - XA * delBK);
// dlnActCoeffdlnN_diag_[iK] += (delAK * XB + XA * delBK - XA * XB) * g1 * (-XB + delBK);
// dlnActCoeffdlnN_diag_[iK] += gggg * ( - 2.0 * XA * XB + delAK * XB + XA * delBK);
// dlnActCoeffdlnN_diag_[iK] += - g1 * XA * XB * (- XB + delBK);
}
dlnActCoeffdlnN_diag_[iK] = XK*dlnActCoeffdlnN_diag_[iK];//-XK;
}
}
//====================================================================================================================
// Update the derivative of the log of the activity coefficients wrt dlnN
/*
* This function will be called to update the internally stored gradients of the
* logarithm of the activity coefficients. These are used in the determination
* of the diffusion coefficients.
*
*/
void MargulesVPSSTP::s_update_dlnActCoeff_dlnN() const
{
size_t iA, iB;
doublereal delAK, delBK;
double XA, XB, g0, g1,XM;
double T = temperature();
double RT = GasConstant*T;
doublereal delAM, delBM;
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++) {
XM = moleFractions_[iM];
for (size_t i = 0; i < numBinaryInteractions_; i++) {
iA = m_pSpecies_A_ij[i];
iB = m_pSpecies_B_ij[i];
delAK = 0.0;
delBK = 0.0;
delAM = 0.0;
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;
}
XA = moleFractions_[iA];
XB = moleFractions_[iB];
g0 = (m_HE_b_ij[i] - T * m_SE_b_ij[i]) / RT;
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);
// double gfac = g0 + g1 * XB;
// double gggg = (delBK - XB) * g1;
// dlnActCoeffdlnN_(iK, iM) += gfac * delAK * ( - XB + delBM);
// dlnActCoeffdlnN_(iK, iM) += gfac * delBK * ( - XA + delAM);
// dlnActCoeffdlnN_(iK, iM) += gfac * (2.0 * XA * XB - delAM * XB - XA * delBM);
// dlnActCoeffdlnN_(iK, iM) += (delAK * XB + XA * delBK - XA * XB) * g1 * (-XB + delBM);
// dlnActCoeffdlnN_(iK, iM) += gggg * ( - 2.0 * XA * XB + delAM * XB + XA * delBM);
// dlnActCoeffdlnN_(iK, iM) += - g1 * XA * XB * (- XB + delBM);
}
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);
doublereal RT = GasConstant * T;
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, -1);
m_pSpecies_B_ij.resize(num, -1);
}
//====================================================================================================================
/*
* Process an XML node called "binaryNeutralSpeciesParameters"
* This node contains all of the parameters necessary to describe
* the Margules Interaction for a single binary interaction
* This function reads the XML file and writes the coefficients
* it finds to an internal data structures.
*/
void MargulesVPSSTP::readXMLBinarySpecies(XML_Node& xmLBinarySpecies)
{
string xname = xmLBinarySpecies.name();
if (xname != "binaryNeutralSpeciesParameters") {
throw CanteraError("MargulesVPSSTP::readXMLBinarySpecies",
"Incorrect name for processing this routine: " + xname);
}
double* charge = DATA_PTR(m_speciesCharge);
string stemp;
size_t nParamsFound;
vector_fp vParams;
string iName = xmLBinarySpecies.attrib("speciesA");
if (iName == "") {
throw CanteraError("MargulesVPSSTP::readXMLBinarySpecies", "no speciesA attrib");
}
string jName = xmLBinarySpecies.attrib("speciesB");
if (jName == "") {
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
*/
size_t iSpecies = speciesIndex(iName);
if (iSpecies == npos) {
return;
}
string ispName = speciesName(iSpecies);
if (charge[iSpecies] != 0) {
throw CanteraError("MargulesVPSSTP::readXMLBinarySpecies", "speciesA charge problem");
}
size_t jSpecies = speciesIndex(jName);
if (jSpecies == npos) {
return;
}
string jspName = speciesName(jSpecies);
if (charge[jSpecies] != 0) {
throw CanteraError("MargulesVPSSTP::readXMLBinarySpecies", "speciesB charge problem");
}
resizeNumInteractions(numBinaryInteractions_ + 1);
size_t iSpot = numBinaryInteractions_ - 1;
m_pSpecies_A_ij[iSpot] = iSpecies;
m_pSpecies_B_ij[iSpot] = jSpecies;
for (size_t iChild = 0; iChild < xmLBinarySpecies.nChildren(); iChild++) {
XML_Node& xmlChild = xmLBinarySpecies.child(iChild);
stemp = xmlChild.name();
string nodeName = lowercase(stemp);
/*
* Process the binary species interaction child elements
*/
if (nodeName == "excessenthalpy") {
/*
* Get the string containing all of the values
*/
ctml::getFloatArray(xmlChild, vParams, true, "toSI", "excessEnthalpy");
nParamsFound = vParams.size();
if (nParamsFound != 2) {
throw CanteraError("MargulesVPSSTP::readXMLBinarySpecies::excessEnthalpy for " + ispName
+ "::" + jspName,
"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
*/
ctml::getFloatArray(xmlChild, vParams, true, "toSI", "excessEntropy");
nParamsFound = vParams.size();
if (nParamsFound != 2) {
throw CanteraError("MargulesVPSSTP::readXMLBinarySpecies::excessEntropy for " + ispName
+ "::" + jspName,
"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
*/
ctml::getFloatArray(xmlChild, vParams, true, "toSI", "excessVolume_Enthalpy");
nParamsFound = vParams.size();
if (nParamsFound != 2) {
throw CanteraError("MargulesVPSSTP::readXMLBinarySpecies::excessVolume_Enthalpy for " + ispName
+ "::" + jspName,
"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
*/
ctml::getFloatArray(xmlChild, vParams, true, "toSI", "excessVolume_Entropy");
nParamsFound = vParams.size();
if (nParamsFound != 2) {
throw CanteraError("MargulesVPSSTP::readXMLBinarySpecies::excessVolume_Entropy for " + ispName
+ "::" + jspName,
"wrong number of params found. Need 2");
}
m_VSE_b_ij[iSpot] = vParams[0];
m_VSE_c_ij[iSpot] = vParams[1];
}
}
}
}
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