void testProblem()
{
double T = 273.15 + 352.0;
vcs_timing_print_lvl = 0;
// Create the phases
std::auto_ptr<ThermoPhase> LiSi_solid(newPhase("Li7Si3_ls.xml",
"Li7Si3_and_Interstitials(S)"));
std::auto_ptr<ThermoPhase> Li_liq(newPhase("Li_Liquid.xml", "Li(L)"));
FixedChemPotSSTP LiFixed("Li", -2.3E7);
MargulesVPSSTP salt("LiKCl_liquid.xml", "MoltenSalt_electrolyte");
// set states
vector_fp x(salt.nSpecies(), 0);
x[0] = 0.7;
x[1] = 1.0 - x[0];
salt.setState_TPX(T, OneAtm, &x[0]);
LiSi_solid->setState_TP(T, OneAtm);
int ee = static_cast<int>(LiSi_solid->nElements());
printf("Number of elements = %d\n", ee);
LiFixed.setState_TP(T, OneAtm);
double um[20];
LiFixed.getChemPotentials(um);
printf(" chem pot = %g\n", um[0]);
double volts = 1.635; // has some Fe in it // test suite
double dg_corr = - volts * Faraday;
printf("dg_corr = %g\n", dg_corr);
Li_liq->getChemPotentials(um);
double um_li_chempot = um[0] + dg_corr;
printf("um_li_chempot = %g\n", um_li_chempot);
LiFixed.setChemicalPotential(um_li_chempot);
MultiPhase mmm;
mmm.addPhase(&salt, 10.);
mmm.addPhase(LiSi_solid.get(), 1.);
mmm.addPhase(&LiFixed, 100.);
int printLvl = 3;
int estimateEquil = 0;
mmm.equilibrate("TP", "vcs", 1e-9, 50000, 100, estimateEquil, printLvl);
std::cout << mmm << std::endl;
appdelete();
}
void ThermoPhase::equilibrate(const std::string& XY, const std::string& solver,
double rtol, int max_steps, int max_iter,
int estimate_equil, int log_level)
{
if (solver == "auto" || solver == "element_potential") {
vector_fp initial_state;
saveState(initial_state);
debuglog("Trying ChemEquil solver\n", log_level);
try {
ChemEquil E;
E.options.maxIterations = max_steps;
E.options.relTolerance = rtol;
bool use_element_potentials = (estimate_equil == 0);
int ret = E.equilibrate(*this, XY.c_str(), use_element_potentials, log_level-1);
if (ret < 0) {
throw CanteraError("ThermoPhase::equilibrate",
"ChemEquil solver failed. Return code: {}", ret);
}
setElementPotentials(E.elementPotentials());
debuglog("ChemEquil solver succeeded\n", log_level);
return;
} catch (std::exception& err) {
debuglog("ChemEquil solver failed.\n", log_level);
debuglog(err.what(), log_level);
restoreState(initial_state);
if (solver == "auto") {
} else {
throw;
}
}
}
if (solver == "auto" || solver == "vcs" || solver == "gibbs") {
MultiPhase M;
M.addPhase(this, 1.0);
M.init();
M.equilibrate(XY, solver, rtol, max_steps, max_iter,
estimate_equil, log_level);
return;
}
if (solver != "auto") {
throw CanteraError("ThermoPhase::equilibrate",
"Invalid solver specified: '{}'", solver);
}
}
TEST_F(OverconstrainedEquil, DISABLED_BasisOptimize2)
{
setup("O H C N Ar");
MultiPhase mphase;
mphase.addPhase(gas.get(), 10.0);
mphase.init();
int usedZeroedSpecies = 0;
std::vector<size_t> orderVectorSpecies;
std::vector<size_t> orderVectorElements;
bool doFormMatrix = true;
vector_fp formRxnMatrix;
size_t nc = BasisOptimize(&usedZeroedSpecies, doFormMatrix, &mphase,
orderVectorSpecies, orderVectorElements,
formRxnMatrix);
ASSERT_EQ(1, (int) nc);
}
/*
* Set a single-phase chemical solution to chemical equilibrium.
* This is a convenience function that uses one or the other of
* the two chemical equilibrium solvers.
*
* @param s The object to set to an equilibrium state
*
* @param XY An integer specifying the two properties to be held
* constant.
*
* @param estimateEquil integer indicating whether the solver
* should estimate its own initial condition.
* If 0, the initial mole fraction vector
* in the %ThermoPhase object is used as the
* initial condition.
* If 1, the initial mole fraction vector
* is used if the element abundances are
* satisfied.
* if -1, the initial mole fraction vector
* is thrown out, and an estimate is
* formulated.
*
* @param printLvl Determines the amount of printing that
* gets sent to stdout from the vcs package
* (Note, you may have to compile with debug
* flags to get some printing).
*
* @param solver The equilibrium solver to use. If solver = 0,
* the ChemEquil solver will be used, and if
* solver = 1, the vcs_MultiPhaseEquil solver will
* be used (slower than ChemEquil,
* but more stable). If solver < 0 (default, then
* ChemEquil will be tried first, and if it fails
* vcs_MultiPhaseEquil will be tried.
*
* @param maxsteps The maximum number of steps to take to find
* the solution.
*
* @param maxiter For the MultiPhaseEquil solver only, this is
* the maximum number of outer temperature or
* pressure iterations to take when T and/or P is
* not held fixed.
*
* @param loglevel Controls amount of diagnostic output. loglevel
* = 0 suppresses diagnostics, and increasingly-verbose
* messages are written as loglevel increases. The
* messages are written to a file in HTML format for viewing
* in a web browser. @see HTML_logs
*/
int vcs_equilibrate(thermo_t& s, const char* XY,
int estimateEquil, int printLvl,
int solver,
doublereal rtol, int maxsteps, int maxiter,
int loglevel)
{
MultiPhase* m = 0;
int retn = 1;
int retnSub = 0;
beginLogGroup("equilibrate", loglevel);
// retry:
addLogEntry("Single-phase equilibrate function");
{
beginLogGroup("arguments");
addLogEntry("phase",s.id());
addLogEntry("XY",XY);
addLogEntry("solver",solver);
addLogEntry("rtol",rtol);
addLogEntry("maxsteps",maxsteps);
addLogEntry("maxiter",maxiter);
addLogEntry("loglevel",loglevel);
endLogGroup("arguments");
}
if (solver == 2) {
m = new MultiPhase;
try {
/*
* Set the kmoles of the phase to 1.0, arbitrarily.
* It actually doesn't matter.
*/
m->addPhase(&s, 1.0);
m->init();
retn = vcs_equilibrate(*m, XY, estimateEquil, printLvl, solver,
rtol, maxsteps, maxiter, loglevel);
if (retn == 1) {
addLogEntry("MultiPhaseEquil solver succeeded.");
} else {
addLogEntry("MultiPhaseEquil solver returned an error code: ", retn);
}
delete m;
} catch (CanteraError& err) {
err.save();
addLogEntry("MultiPhaseEquil solver failed.");
delete m;
throw err;
}
} else if (solver == 1) {
m = new MultiPhase;
try {
m->addPhase(&s, 1.0);
m->init();
(void) equilibrate(*m, XY, rtol, maxsteps, maxiter, loglevel-1);
if (loglevel > 0) {
addLogEntry("MultiPhaseEquil solver succeeded.");
}
delete m;
retn = 1;
} catch (CanteraError& err) {
err.save();
if (loglevel > 0) {
addLogEntry("MultiPhaseEquil solver failed.");
}
delete m;
throw err;
}
} else if (solver == 0) {
ChemEquil* e = new ChemEquil;
try {
e->options.maxIterations = maxsteps;
e->options.relTolerance = rtol;
bool useThermoPhaseElementPotentials = false;
if (estimateEquil == 0) {
useThermoPhaseElementPotentials = true;
}
retnSub = e->equilibrate(s, XY,
useThermoPhaseElementPotentials, loglevel-1);
if (retnSub < 0) {
if (loglevel > 0) {
addLogEntry("ChemEquil solver failed.");
}
delete e;
throw CanteraError("equilibrate",
"ChemEquil equilibrium solver failed");
}
retn = 1;
s.setElementPotentials(e->elementPotentials());
delete e;
if (loglevel > 0) {
addLogEntry("ChemEquil solver succeeded.");
}
} catch (CanteraError& err) {
err.save();
if (loglevel > 0) {
addLogEntry("ChemEquil solver failed.");
}
delete e;
throw err;
}
} else {
throw CanteraError("vcs_equilibrate",
"unknown solver");
}
/*
* We are here only for a success
*/
endLogGroup("equilibrate");
return retn;
}
int main(int argc, char** argv)
{
#if defined(_MSC_VER) && _MSC_VER < 1900
_set_output_format(_TWO_DIGIT_EXPONENT);
#endif
suppress_deprecation_warnings();
int numSucc = 0;
int numFail = 0;
int printLvl = 1;
string inputFile = "HMW_NaCl.xml";
VCS_SOLVE::disableTiming();
/*
* Process the command line arguments
*/
if (argc > 1) {
string tok;
for (int j = 1; j < argc; j++) {
tok = string(argv[j]);
if (tok[0] == '-') {
int nopt = static_cast<int>(tok.size());
for (int n = 1; n < nopt; n++) {
if (!strcmp(tok.c_str() + 1, "help_cmdfile")) {
} else if (tok[n] == 'h') {
printUsage();
exit(1);
} else if (tok[n] == 'd') {
printLvl = 2;
int lvl = 2;
if (j < (argc - 1)) {
string tokla = string(argv[j+1]);
if (strlen(tokla.c_str()) > 0) {
lvl = atoi(tokla.c_str());
n = nopt - 1;
j += 1;
if (lvl >= 0) {
printLvl = lvl;
}
}
}
} else {
printUsage();
exit(1);
}
}
} else if (inputFile == "HMW_NaCl.xml") {
inputFile = tok;
} else {
printUsage();
exit(1);
}
}
}
try {
int estimateEquil = -1;
double T = 298.15;
double pres = OneAtm;
// Initialize the individual phases
HMWSoln hmw(inputFile, "");
size_t kk = hmw.nSpecies();
vector_fp Xmol(kk, 0.0);
size_t iH2OL = hmw.speciesIndex("H2O(L)");
Xmol[iH2OL] = 1.0;
hmw.setState_TPX(T, pres, Xmol.data());
ThermoPhase* gas = newPhase("gas.xml");
kk = gas->nSpecies();
Xmol.resize(kk, 0.0);
for (size_t i = 0; i < kk; i++) {
Xmol[i] = 0.0;
}
size_t iN2 = gas->speciesIndex("N2");
Xmol[iN2] = 1.0;
gas->setState_TPX(T, pres, Xmol.data());
StoichSubstance ss("NaCl_Solid.xml", "");
ss.setState_TP(T, pres);
// Construct the multiphase object
MultiPhase* mp = new MultiPhase();
mp->addPhase(&hmw, 2.0);
mp->addPhase(gas, 4.0);
mp->addPhase(&ss, 5.0);
try {
mp->equilibrate("TP", "vcs", 1e-9, 50000, 100, estimateEquil, printLvl);
cout << *mp;
numSucc++;
} catch (CanteraError& err) {
cout << *mp;
std::cerr << err.what() << std::endl;
cerr << "ERROR: MultiEquil equilibration step failed at "
<< " T = " << T
<< " Pres = " << pres
<< endl;
cout << "ERROR: MultiEqiul equilibration step failed at "
<< " T = " << T
<< " Pres = " << pres
<< endl;
exit(-1);
}
cout << "NUMBER OF SUCCESSES = " << numSucc << endl;
cout << "NUMBER OF FAILURES = " << numFail << endl;
return numFail;
} catch (CanteraError& err) {
std::cerr << err.what() << std::endl;
cerr << "ERROR: program terminating due to unforeseen circumstances." << endl;
return -1;
}
}
int vcs_equilibrate(thermo_t& s, const char* XY,
int estimateEquil, int printLvl,
int solver,
doublereal rtol, int maxsteps, int maxiter,
int loglevel)
{
warn_deprecated("vcs_equilibrate", "Use ThermoPhase::equilibrate instead. "
"To be removed after Cantera 2.2.");
MultiPhase* m = 0;
int retn = 1;
if (solver == 2) {
m = new MultiPhase;
try {
/*
* Set the kmoles of the phase to 1.0, arbitrarily.
* It actually doesn't matter.
*/
m->addPhase(&s, 1.0);
m->init();
retn = vcs_equilibrate(*m, XY, estimateEquil, printLvl, solver,
rtol, maxsteps, maxiter, loglevel);
delete m;
} catch (CanteraError& err) {
err.save();
delete m;
throw err;
}
} else if (solver == 1) {
m = new MultiPhase;
try {
m->addPhase(&s, 1.0);
m->init();
(void) equilibrate(*m, XY, rtol, maxsteps, maxiter, loglevel-1);
delete m;
retn = 1;
} catch (CanteraError& err) {
err.save();
delete m;
throw err;
}
} else if (solver == 0) {
ChemEquil* e = new ChemEquil;
try {
e->options.maxIterations = maxsteps;
e->options.relTolerance = rtol;
bool useThermoPhaseElementPotentials = false;
if (estimateEquil == 0) {
useThermoPhaseElementPotentials = true;
}
int retnSub = e->equilibrate(s, XY,
useThermoPhaseElementPotentials, loglevel-1);
if (retnSub < 0) {
delete e;
throw CanteraError("equilibrate",
"ChemEquil equilibrium solver failed");
}
retn = 1;
s.setElementPotentials(e->elementPotentials());
delete e;
} catch (CanteraError& err) {
err.save();
delete e;
throw err;
}
} else {
throw CanteraError("vcs_equilibrate",
"unknown solver");
}
/*
* We are here only for a success
*/
return retn;
}
/*
* Set a single-phase chemical solution to chemical equilibrium.
* This is a convenience function that uses one or the other of
* the two chemical equilibrium solvers.
*
* @param s The object to set to an equilibrium state
*
* @param XY An integer specifying the two properties to be held
* constant.
*
* @param solver The equilibrium solver to use. If solver = 0,
* the ChemEquil solver will be used, and if solver = 1, the
* MultiPhaseEquil solver will be used (slower than ChemEquil,
* but more stable). If solver < 0 (default, then ChemEquil will
* be tried first, and if it fails MultiPhaseEquil will be tried.
*
* @param maxsteps The maximum number of steps to take to find
* the solution.
*
* @param maxiter For the MultiPhaseEquil solver only, this is
* the maximum number of outer temperature or pressure iterations
* to take when T and/or P is not held fixed.
*
* @param loglevel Controls amount of diagnostic output. loglevel
* = 0 suppresses diagnostics, and increasingly-verbose messages
* are written as loglevel increases. The messages are written to
* a file in HTML format for viewing in a web browser.
* @see HTML_logs
*
* @ingroup equil
*/
int equilibrate(thermo_t& s, const char* XY, int solver,
doublereal rtol, int maxsteps, int maxiter, int loglevel) {
MultiPhase* m = 0;
ChemEquil* e = 0;
bool redo = true;
int retn = -1;
int nAttempts = 0;
int retnSub = 0;
if (loglevel > 0) {
beginLogGroup("equilibrate", loglevel);
addLogEntry("Single-phase equilibrate function");
{
beginLogGroup("arguments");
addLogEntry("phase",s.id());
addLogEntry("XY",XY);
addLogEntry("solver",solver);
addLogEntry("rtol",rtol);
addLogEntry("maxsteps",maxsteps);
addLogEntry("maxiter",maxiter);
addLogEntry("loglevel",loglevel);
endLogGroup("arguments");
}
}
while (redo) {
if (solver >= 2) {
#ifdef WITH_VCSNONIDEAL
int printLvlSub = 0;
int estimateEquil = 0;
m = new MultiPhase;
try {
m->addPhase(&s, 1.0);
m->init();
nAttempts++;
vcs_equilibrate(*m, XY, estimateEquil, printLvlSub, solver,
rtol, maxsteps, maxiter, loglevel-1);
redo = false;
if (loglevel > 0)
addLogEntry("VCSnonideal solver succeeded.");
delete m;
retn = nAttempts;
}
catch (CanteraError &err) {
if (loglevel > 0)
addLogEntry("VCSnonideal solver failed.");
delete m;
if (nAttempts < 2) {
if (loglevel > 0)
addLogEntry("Trying single phase ChemEquil solver.");
solver = -1;
}
else {
if (loglevel > 0)
endLogGroup("equilibrate");
throw err;
}
}
#else
throw CanteraError("equilibrate",
"VCSNonIdeal solver called, but not compiled");
#endif
} else if (solver == 1) {
m = new MultiPhase;
try {
m->addPhase(&s, 1.0);
m->init();
nAttempts++;
(void) equilibrate(*m, XY, rtol, maxsteps, maxiter, loglevel-1);
redo = false;
if (loglevel > 0)
addLogEntry("MultiPhaseEquil solver succeeded.");
delete m;
retn = nAttempts;
}
catch (CanteraError &err) {
if (loglevel > 0)
addLogEntry("MultiPhaseEquil solver failed.");
delete m;
if (nAttempts < 2) {
if (loglevel > 0)
addLogEntry("Trying single phase ChemEquil solver.");
solver = -1;
}
else {
if (loglevel > 0)
endLogGroup("equilibrate");
throw err;
}
}
}
else { // solver <= 0
/*
* Call the element potential solver
*/
e = new ChemEquil;
try {
e->options.maxIterations = maxsteps;
e->options.relTolerance = rtol;
nAttempts++;
bool useThermoPhaseElementPotentials = true;
retnSub = e->equilibrate(s,XY,
useThermoPhaseElementPotentials, loglevel-1);
if (retnSub < 0) {
if (loglevel > 0)
addLogEntry("ChemEquil solver failed.");
if (nAttempts < 2) {
if (loglevel > 0)
addLogEntry("Trying MultiPhaseEquil solver.");
solver = 1;
} else {
throw CanteraError("equilibrate",
"Both equilibrium solvers failed");
}
}
retn = nAttempts;
s.setElementPotentials(e->elementPotentials());
redo = false;
delete e;
if (loglevel > 0)
addLogEntry("ChemEquil solver succeeded.");
}
catch (CanteraError &err) {
delete e;
if (loglevel > 0)
addLogEntry("ChemEquil solver failed.");
// If ChemEquil fails, try the MultiPhase solver
if (solver < 0) {
if (loglevel > 0)
addLogEntry("Trying MultiPhaseEquil solver.");
solver = 1;
}
else {
redo = false;
if (loglevel > 0)
endLogGroup("equilibrate");
throw err;
}
}
}
} // while (redo)
/*
* We are here only for a success
*/
if (loglevel > 0)
endLogGroup("equilibrate");
return retn;
}
int equilibrate(thermo_t& s, const char* XY, int solver,
doublereal rtol, int maxsteps, int maxiter, int loglevel)
{
bool redo = true;
int retn = -1;
int nAttempts = 0;
int retnSub = 0;
if (loglevel > 0) {
beginLogGroup("equilibrate", loglevel);
addLogEntry("Single-phase equilibrate function");
{
beginLogGroup("arguments");
addLogEntry("phase",s.id());
addLogEntry("XY",XY);
addLogEntry("solver",solver);
addLogEntry("rtol",rtol);
addLogEntry("maxsteps",maxsteps);
addLogEntry("maxiter",maxiter);
addLogEntry("loglevel",loglevel);
endLogGroup("arguments");
}
}
while (redo) {
if (solver >= 2) {
int printLvlSub = 0;
int estimateEquil = 0;
try {
MultiPhase m;
m.addPhase(&s, 1.0);
m.init();
nAttempts++;
vcs_equilibrate(m, XY, estimateEquil, printLvlSub, solver,
rtol, maxsteps, maxiter, loglevel-1);
redo = false;
if (loglevel > 0) {
addLogEntry("VCSnonideal solver succeeded.");
}
retn = nAttempts;
} catch (CanteraError& err) {
err.save();
if (loglevel > 0) {
addLogEntry("VCSnonideal solver failed.");
}
if (nAttempts < 2) {
if (loglevel > 0) {
addLogEntry("Trying single phase ChemEquil solver.");
}
solver = -1;
} else {
if (loglevel > 0) {
endLogGroup("equilibrate");
}
throw err;
}
}
} else if (solver == 1) {
try {
MultiPhase m;
m.addPhase(&s, 1.0);
m.init();
nAttempts++;
equilibrate(m, XY, rtol, maxsteps, maxiter, loglevel-1);
redo = false;
if (loglevel > 0) {
addLogEntry("MultiPhaseEquil solver succeeded.");
}
retn = nAttempts;
} catch (CanteraError& err) {
err.save();
if (loglevel > 0) {
addLogEntry("MultiPhaseEquil solver failed.");
}
if (nAttempts < 2) {
if (loglevel > 0) {
addLogEntry("Trying single phase ChemEquil solver.");
}
solver = -1;
} else {
if (loglevel > 0) {
endLogGroup("equilibrate");
}
throw err;
}
}
} else { // solver <= 0
/*
* Call the element potential solver
*/
try {
ChemEquil e;
e.options.maxIterations = maxsteps;
e.options.relTolerance = rtol;
nAttempts++;
bool useThermoPhaseElementPotentials = true;
retnSub = e.equilibrate(s, XY, useThermoPhaseElementPotentials,
loglevel-1);
if (retnSub < 0) {
if (loglevel > 0) {
addLogEntry("ChemEquil solver failed.");
}
if (nAttempts < 2) {
if (loglevel > 0) {
addLogEntry("Trying MultiPhaseEquil solver.");
}
solver = 1;
} else {
throw CanteraError("equilibrate",
"Both equilibrium solvers failed");
}
}
retn = nAttempts;
s.setElementPotentials(e.elementPotentials());
redo = false;
if (loglevel > 0) {
addLogEntry("ChemEquil solver succeeded.");
}
}
catch (CanteraError& err) {
err.save();
if (loglevel > 0) {
addLogEntry("ChemEquil solver failed.");
}
// If ChemEquil fails, try the MultiPhase solver
if (solver < 0) {
if (loglevel > 0) {
addLogEntry("Trying MultiPhaseEquil solver.");
}
solver = 1;
} else {
redo = false;
if (loglevel > 0) {
endLogGroup("equilibrate");
}
throw err;
}
}
}
} // while (redo)
/*
* We are here only for a success
*/
if (loglevel > 0) {
endLogGroup("equilibrate");
}
return retn;
}