void SurfPhase::
setCoveragesByName(std::string cov) {
int kk = nSpecies();
int k;
compositionMap cc;
for (k = 0; k < kk; k++) {
cc[speciesName(k)] = -1.0;
}
parseCompString(cov, cc);
doublereal c;
vector_fp cv(kk, 0.0);
bool ifound = false;
for (k = 0; k < kk; k++) {
c = cc[speciesName(k)];
if (c > 0.0) {
ifound = true;
cv[k] = c;
}
}
if (!ifound) {
throw CanteraError("SurfPhase::setCoveragesByName",
"Input coverages are all zero or negative");
}
setCoverages(DATA_PTR(cv));
}
shared_ptr<Species> make_shomate2_species(const std::string& name,
const std::string& composition, const double* shomate_coeffs)
{
auto species = make_shared<Species>(name, parseCompString(composition));
species->thermo.reset(new ShomatePoly2(200, 3500, 101325, shomate_coeffs));
return species;
}
shared_ptr<Species> make_const_cp_species(const std::string& name,
const std::string& composition, double T0, double h0, double s0, double cp)
{
auto species = make_shared<Species>(name, parseCompString(composition));
double coeffs[] = {T0, h0, s0, cp};
species->thermo.reset(new ConstCpPoly(200, 3500, 101325, coeffs));
return species;
}
void Phase::setMassFractionsByName(const std::string& y) {
compositionMap yy;
int kk = nSpecies();
for (int k = 0; k < kk; k++) {
yy[speciesName(k)] = -1.0;
}
parseCompString(y, yy);
setMassFractionsByName(yy);
}
/*
* setMolalitiesByNames()
*
* Set the molalities of the solutes by name
*/
void MolalityVPSSTP::setMolalitiesByName(const std::string& x)
{
compositionMap xx;
for (size_t k = 0; k < nSpecies(); k++) {
xx[speciesName(k)] = -1.0;
}
parseCompString(x, xx);
setMolalitiesByName(xx);
}
shared_ptr<Species> make_species(const std::string& name,
const std::string& composition, double h298,
double T1, double mu1, double T2, double mu2, double pref=101325)
{
auto species = make_shared<Species>(name, parseCompString(composition));
double coeffs[] = {2, h298, T1, mu1*GasConstant*T1, T2, mu2*GasConstant*T2};
species->thermo.reset(new Mu0Poly(200, 3500, pref, coeffs));
return species;
}
ConstructFromScratch()
: sH2O(make_species("H2O", "H:2 O:1", h2o_nasa_coeffs))
, sH2(make_species("H2", "H:2", h2_nasa_coeffs))
, sO2(make_species("O2", "O:2", o2_nasa_coeffs))
, sOH(make_species("OH", "H:1 O:1", oh_nasa_coeffs))
, sCO(make_species("CO", "C:1 O:1", o2_nasa_coeffs))
, sCO2(new Species("CO2", parseCompString("C:1 O:2")))
{
sCO2->thermo.reset(new ShomatePoly2(200, 3500, 101325, co2_shomate_coeffs));
}
void Phase::setMoleFractionsByName(const std::string& x)
{
size_t kk = nSpecies();
compositionMap xx;
for (size_t k = 0; k < kk; k++) {
xx[speciesName(k)] = -1.0;
}
parseCompString(x, xx);
setMoleFractionsByName(xx);
}
TEST(PureFluidFromScratch, CarbonDioxide)
{
PureFluidPhase p;
auto sCO2 = make_shared<Species>("CO2", parseCompString("C:1 O:2"));
sCO2->thermo.reset(new ShomatePoly2(200, 6000, 101325, co2_shomate_coeffs));
p.addSpecies(sCO2);
p.setSubstance("carbondioxide");
p.initThermo();
p.setState_Tsat(280, 0.5);
EXPECT_NEAR(p.pressure(), 4160236.987, 1e-2);
}
TEST(IonsFromNeutralConstructor, fromScratch)
{
auto neutral = make_shared<MargulesVPSSTP>();
auto sKCl = make_shomate_species("KCl(L)", "K:1 Cl:1", kcl_shomate_coeffs);
neutral->addSpecies(sKCl);
std::unique_ptr<PDSS_ConstVol> ssKCl(new PDSS_ConstVol());
ssKCl->setMolarVolume(0.03757);
neutral->installPDSS(0, std::move(ssKCl));
neutral->initThermo();
IonsFromNeutralVPSSTP p;
p.setNeutralMoleculePhase(neutral);
auto sKp = make_shared<Species>("K+", parseCompString("K:1"), 1);
auto sClm = make_shared<Species>("Cl-", parseCompString("Cl:1"), -1);
sClm->extra["special_species"] = true;
p.addSpecies(sKp);
p.addSpecies(sClm);
std::unique_ptr<PDSS_IonsFromNeutral> ssKp(new PDSS_IonsFromNeutral());
std::unique_ptr<PDSS_IonsFromNeutral> ssClm(new PDSS_IonsFromNeutral());
ssKp->setNeutralSpeciesMultiplier("KCl(L)", 1.2);
ssClm->setNeutralSpeciesMultiplier("KCl(L)", 1.5);
ssClm->setSpecialSpecies();
p.installPDSS(0, std::move(ssKp));
p.installPDSS(1, std::move(ssClm));
p.initThermo();
ASSERT_EQ((int) p.nSpecies(), 2);
p.setState_TPX(500, 2e5, "K+:0.1, Cl-:0.1");
vector_fp mu(p.nSpecies());
p.getChemPotentials(mu.data());
// Values for regression testing only -- same as XML test
EXPECT_NEAR(p.density(), 1984.3225978174073, 1e-6);
EXPECT_NEAR(p.enthalpy_mass(), -8035317241137.971, 1e-1);
EXPECT_NEAR(mu[0], -4.66404010e+08, 1e1);
EXPECT_NEAR(mu[1], -2.88157298e+06, 1e-1);
}
void Phase::setMoleFractionsByName(const std::string& x) {
compositionMap xx;
int kk = nSpecies();
for (int k = 0; k < kk; k++) {
xx[speciesName(k)] = -1.0;
}
parseCompString(x, xx);
setMoleFractionsByName(xx);
//int kk = nSpecies();
//vector_fp mf(kk);
//for (int k = 0; k < kk; k++) {
// mf[k] = xx[speciesName(k)];
//}
//setMoleFractions(mf.begin());
}
TEST(LatticeSolidPhase, fromScratch)
{
auto base = make_shared<StoichSubstance>();
base->setName("Li7Si3(S)");
base->setDensity(1390.0);
auto sLi7Si3 = make_shomate2_species("Li7Si3(S)", "Li:7 Si:3", li7si3_shomate_coeffs);
base->addSpecies(sLi7Si3);
base->initThermo();
auto interstital = make_shared<LatticePhase>();
interstital->setName("Li7Si3_Interstitial");
auto sLii = make_const_cp_species("Li(i)", "Li:1", 298.15, 0, 2e4, 2e4);
auto sVac = make_const_cp_species("V(i)", "", 298.15, 8.98e4, 0, 0);
sLii->extra["molar_volume"] = 0.2;
interstital->setSiteDensity(10.46344);
interstital->addSpecies(sLii);
interstital->addSpecies(sVac);
interstital->initThermo();
interstital->setMoleFractionsByName("Li(i):0.01 V(i):0.99");
LatticeSolidPhase p;
p.addLattice(base);
p.addLattice(interstital);
p.setLatticeStoichiometry(parseCompString("Li7Si3(S):1.0 Li7Si3_Interstitial:1.0"));
p.initThermo();
p.setState_TP(725, 10 * OneAtm);
// Regression test based on modified version of Li7Si3_ls.xml
EXPECT_NEAR(p.enthalpy_mass(), -2077821.9295456698, 1e-6);
double mu_ref[] = {-4.62717474e+08, -4.64248485e+07, 1.16370186e+05};
double vol_ref[] = {0.09557086, 0.2, 0.09557086};
vector_fp mu(p.nSpecies());
vector_fp vol(p.nSpecies());
p.getChemPotentials(mu.data());
p.getPartialMolarVolumes(vol.data());
for (size_t k = 0; k < p.nSpecies(); k++) {
EXPECT_NEAR(mu[k], mu_ref[k], 1e-7*fabs(mu_ref[k]));
EXPECT_NEAR(vol[k], vol_ref[k], 1e-7);
}
}
FixedChemPotSSTP::FixedChemPotSSTP(const std::string& Ename, doublereal val) :
chemPot_(0.0)
{
std::string pname = Ename + "Fixed";
setID(pname);
setName(pname);
setNDim(3);
addElement(Ename);
auto sp = make_shared<Species>(pname, parseCompString(Ename + ":1.0"));
double c[4] = {298.15, val, 0.0, 0.0};
shared_ptr<SpeciesThermoInterpType> stit(
newSpeciesThermoInterpType("const_cp", 0.1, 1e30, OneAtm, c));
sp->thermo = stit;
addSpecies(sp);
initThermo();
m_p0 = OneAtm;
m_tlast = 298.15;
setChemicalPotential(val);
// Create an XML_Node entry for this species
XML_Node s("species", 0);
s.addAttribute("name", pname);
std::string aaS = Ename + ":1";
s.addChild("atomArray", aaS);
XML_Node& tt = s.addChild("thermo");
XML_Node& ss = tt.addChild("Simple");
ss.addAttribute("Pref", "1 bar");
ss.addAttribute("Tmax", "5000.");
ss.addAttribute("Tmin", "100.");
ss.addChild("t0", "298.15");
ss.addChild("cp0", "0.0");
std::string sval = fp2str(val);
ss.addChild("h", sval);
ss.addChild("s", "0.0");
saveSpeciesData(0, &s);
}
void Phase::setMassFractionsByName(const std::string& y)
{
setMassFractionsByName(parseCompString(y));
}
void Phase::setMoleFractionsByName(const std::string& x)
{
setMoleFractionsByName(parseCompString(x));
}
bool installSpecies(size_t k, const XML_Node& s, thermo_t& th,
SpeciesThermo* spthermo_ptr, int rule,
XML_Node* phaseNode_ptr,
VPSSMgr* vpss_ptr,
SpeciesThermoFactory* factory)
{
std::string xname = s.name();
if (xname != "species") {
throw CanteraError("installSpecies",
"Unexpected XML name of species XML_Node: " + xname);
}
if (rule) {
th.ignoreUndefinedElements();
}
// get the composition of the species
const XML_Node& a = s.child("atomArray");
map<string,string> comp;
getMap(a, comp);
// construct a vector of atom numbers for each element in phase th. Elements
// not declared in the species (i.e., not in map comp) will have zero
// entries in the vector.
size_t nel = th.nElements();
vector_fp ecomp(nel, 0.0);
compositionMap comp_map = parseCompString(a.value());
for (size_t m = 0; m < nel; m++) {
std::string& es = comp[th.elementName(m)];
if (!es.empty()) {
ecomp[m] = fpValueCheck(es);
}
}
// get the species charge, if any. Note that the charge need
// not be explicitly specified if special element 'E'
// (electron) is one of the elements.
doublereal chrg = 0.0;
if (s.hasChild("charge")) {
chrg = getFloat(s, "charge");
}
// get the species size, if any. (This is used by surface
// phases to represent how many sites a species occupies.)
doublereal sz = 1.0;
if (s.hasChild("size")) {
sz = getFloat(s, "size");
}
if (vpss_ptr) {
th.addUniqueSpecies(s["name"], &ecomp[0], chrg, sz);
VPStandardStateTP* vp_ptr = dynamic_cast<VPStandardStateTP*>(&th);
vp_ptr->createInstallPDSS(k, s, phaseNode_ptr);
} else {
SpeciesThermoInterpType* st = newSpeciesThermoInterpType(s);
Species sp(s["name"], comp_map, st, chrg, sz);
// Read gas-phase transport data, if provided
if (s.hasChild("transport") &&
s.child("transport")["model"] == "gas_transport") {
XML_Node& tr = s.child("transport");
string geometry, dummy;
getString(tr, "geometry", geometry, dummy);
double diam = getFloat(tr, "LJ_diameter");
double welldepth = getFloat(tr, "LJ_welldepth");
double dipole = 0.0;
getOptionalFloat(tr, "dipoleMoment", dipole);
double polar = 0.0;
getOptionalFloat(tr, "polarizability", polar);
double rot = 0.0;
getOptionalFloat(tr, "rotRelax", rot);
double acentric = 0.0;
getOptionalFloat(tr, "acentric_factor", acentric);
GasTransportData* gastran = new GasTransportData;
gastran->setCustomaryUnits(sp.name, geometry, diam, welldepth,
dipole, polar, rot, acentric);
sp.transport.reset(gastran);
gastran->validate(sp);
}
th.addSpecies(sp);
}
return true;
}
void Phase::setMassFractionsByName(const std::string& y)
{
compositionMap c = parseCompString(y, speciesNames());
setMassFractionsByName(c);
}
void Phase::setMoleFractionsByName(const std::string& x)
{
compositionMap c = parseCompString(x, speciesNames());
setMoleFractionsByName(c);
}
void MolalityVPSSTP::setMolalitiesByName(const std::string& x)
{
compositionMap xx = parseCompString(x, speciesNames());
setMolalitiesByName(xx);
}
bool checkElectrochemReaction(const XML_Node& p, Kinetics& kin, const XML_Node& r)
{
// If other phases are involved in the reaction mechanism, they must be
// listed in a 'phaseArray' child element. Homogeneous mechanisms do not
// need to include a phaseArray element.
vector<string> phase_ids;
if (p.hasChild("phaseArray")) {
const XML_Node& pa = p.child("phaseArray");
getStringArray(pa, phase_ids);
}
phase_ids.push_back(p["id"]);
// Get reaction product and reactant information
Composition reactants = parseCompString(r.child("reactants").value());
Composition products = parseCompString(r.child("products").value());
// If the reaction has undeclared species don't perform electrochemical check
for (const auto& sp : reactants) {
if (kin.kineticsSpeciesIndex(sp.first) == npos) {
return true;
}
}
for (const auto& sp : products) {
if (kin.kineticsSpeciesIndex(sp.first) == npos) {
return true;
}
}
// Initialize the electron counter for each phase
std::vector<double> e_counter(phase_ids.size(), 0.0);
// Find the amount of electrons in the products for each phase
for (const auto& sp : products) {
const ThermoPhase& ph = kin.speciesPhase(sp.first);
size_t k = ph.speciesIndex(sp.first);
double stoich = sp.second;
for (size_t m = 0; m < phase_ids.size(); m++) {
if (phase_ids[m] == ph.id()) {
e_counter[m] += stoich * ph.charge(k);
break;
}
}
}
// Subtract the amount of electrons in the reactants for each phase
for (const auto& sp : reactants) {
const ThermoPhase& ph = kin.speciesPhase(sp.first);
size_t k = ph.speciesIndex(sp.first);
double stoich = sp.second;
for (size_t m = 0; m < phase_ids.size(); m++) {
if (phase_ids[m] == ph.id()) {
e_counter[m] -= stoich * ph.charge(k);
break;
}
}
}
// If the electrons change phases then the reaction is electrochemical
bool echemical = false;
for(size_t m = 0; m < phase_ids.size(); m++) {
if (fabs(e_counter[m]) > 1e-4) {
echemical = true;
break;
}
}
// If the reaction is electrochemical, ensure the reaction is identified as
// electrochemical. If not already specified beta is assumed to be 0.5
std::string type = ba::to_lower_copy(r["type"]);
if (!r.child("rateCoeff").hasChild("electrochem")) {
if ((type != "butlervolmer_noactivitycoeffs" &&
type != "butlervolmer" &&
type != "surfaceaffinity") &&
echemical) {
XML_Node& f = r.child("rateCoeff").addChild("electrochem","");
f.addAttribute("beta",0.5);
}
}
return true;
}
