void IdealMolalSoln::getPartialMolarEntropies(doublereal* sbar) const
{
getEntropy_R(sbar);
calcMolalities();
if (IMS_typeCutoff_ == 0) {
for (size_t k = 1; k < m_kk; k++) {
doublereal mm = std::max(SmallNumber, m_molalities[k]);
sbar[k] -= GasConstant * log(mm);
}
double xmolSolvent = moleFraction(0);
sbar[0] -= (GasConstant * (xmolSolvent - 1.0) / xmolSolvent);
} else {
// Update the activity coefficients, This also update the internally
// stored molalities.
s_updateIMS_lnMolalityActCoeff();
// First we will add in the obvious dependence on the T term out front
// of the log activity term
doublereal mm;
for (size_t k = 1; k < m_kk; k++) {
mm = std::max(SmallNumber, m_molalities[k]);
sbar[k] -= GasConstant * (log(mm) + IMS_lnActCoeffMolal_[k]);
}
double xmolSolvent = moleFraction(0);
mm = std::max(SmallNumber, xmolSolvent);
sbar[0] -= GasConstant *(log(mm) + IMS_lnActCoeffMolal_[0]);
}
}
void IdealMolalSoln::getActivities(doublereal* ac) const
{
_updateStandardStateThermo();
// Update the molality array, m_molalities(). This requires an update due to
// mole fractions
if (IMS_typeCutoff_ == 0) {
calcMolalities();
for (size_t k = 0; k < m_kk; k++) {
ac[k] = m_molalities[k];
}
double xmolSolvent = moleFraction(0);
// Limit the activity coefficient to be finite as the solvent mole
// fraction goes to zero.
xmolSolvent = std::max(m_xmolSolventMIN, xmolSolvent);
ac[0] = exp((xmolSolvent - 1.0)/xmolSolvent);
} else {
s_updateIMS_lnMolalityActCoeff();
// Now calculate the array of activities.
for (size_t k = 1; k < m_kk; k++) {
ac[k] = m_molalities[k] * exp(IMS_lnActCoeffMolal_[k]);
}
double xmolSolvent = moleFraction(0);
ac[0] = exp(IMS_lnActCoeffMolal_[0]) * xmolSolvent;
}
}
void IdealSolnGasVPSS::getActivityConcentrations(doublereal* c) const {
if (m_idealGas) {
getConcentrations(c);
} else {
int k;
const vector_fp& vss = m_VPSS_ptr->standardVolumes();
switch (m_formGC) {
case 0:
for (k = 0; k < m_kk; k++) {
c[k] = moleFraction(k);
}
break;
case 1:
for (k = 0; k < m_kk; k++) {
c[k] = moleFraction(k) / vss[k];
}
break;
case 2:
for (k = 0; k < m_kk; k++) {
c[k] = moleFraction(k) / vss[0];
}
break;
}
}
}
/*!
* \brief Return the molar density of a fluid phase [mol/m^3].
*/
Scalar molarDensity(unsigned phaseIdx) const
{
const auto& rho = density(phaseIdx);
if (phaseIdx == waterPhaseIdx)
return rho/FluidSystem::molarMass(waterCompIdx, pvtRegionIdx_);
return
rho*(moleFraction(phaseIdx, gasCompIdx)/FluidSystem::molarMass(gasCompIdx, pvtRegionIdx_)
+ moleFraction(phaseIdx, oilCompIdx)/FluidSystem::molarMass(oilCompIdx, pvtRegionIdx_));
}
/*!
* \brief Return the fugacity of a component in a fluid phase [Pa].
*/
Scalar fugacity(unsigned phaseIdx, unsigned compIdx) const
{
return
fugacityCoefficient(phaseIdx, compIdx)
*moleFraction(phaseIdx, compIdx)
*pressure(phaseIdx);
}
/*!
* \brief Return the partial molar density of a fluid phase [kg / mol].
*/
Scalar averageMolarMass(unsigned phaseIdx) const
{
Scalar result(0.0);
for (unsigned compIdx = 0; compIdx < numComponents; ++ compIdx)
result += FluidSystem::molarMass(compIdx, pvtRegionIdx_)*moleFraction(phaseIdx, compIdx);
return result;
}
void MaskellSolidSolnPhase::getActivityConcentrations(doublereal* c) const
{
getActivityCoefficients(c);
for (size_t sp = 0; sp < m_kk; ++sp) {
c[sp] *= moleFraction(sp);
}
}
doublereal Phase::chargeDensity() const
{
doublereal cdens = 0.0;
for (size_t k = 0; k < m_kk; k++) {
cdens += charge(k)*moleFraction(k);
}
return cdens * Faraday;
}
void IdealGasPhase::getChemPotentials(doublereal* mu) const
{
getStandardChemPotentials(mu);
for (size_t k = 0; k < m_kk; k++) {
double xx = std::max(SmallNumber, moleFraction(k));
mu[k] += RT() * log(xx);
}
}
doublereal MaskellSolidSolnPhase::enthalpy_mole() const
{
_updateThermo();
const doublereal h0 = RT() * mean_X(m_h0_RT);
const doublereal r = moleFraction(product_species_index);
const doublereal fmval = fm(r);
return h0 + r * fmval * h_mixing;
}
doublereal Phase::elementalMoleFraction(const size_t m) const
{
checkElementIndex(m);
double denom = 0;
for (size_t k = 0; k < m_kk; k++) {
double atoms = 0;
for (size_t j = 0; j < nElements(); j++) {
atoms += nAtoms(k, j);
}
denom += atoms * moleFraction(k);
}
doublereal numerator = 0.0;
for (size_t k = 0; k != m_kk; ++k) {
numerator += nAtoms(k, m) * moleFraction(k);
}
return numerator / denom;
}
void LatticePhase::getPartialMolarEntropies(doublereal* sbar) const
{
const vector_fp& _s = entropy_R_ref();
for (size_t k = 0; k < m_kk; k++) {
double xx = std::max(SmallNumber, moleFraction(k));
sbar[k] = GasConstant * (_s[k] - log(xx));
}
}
void MolalityVPSSTP::getActivityCoefficients(doublereal* ac) const
{
getMolalityActivityCoefficients(ac);
AssertThrow(m_indexSolvent==0, "MolalityVPSSTP::getActivityCoefficients");
double xmolSolvent = std::max(moleFraction(m_indexSolvent), m_xmolSolventMIN);
for (size_t k = 1; k < m_kk; k++) {
ac[k] /= xmolSolvent;
}
}
void IdealSolnGasVPSS::getPartialMolarEntropies(doublereal* sbar) const {
getEntropy_R(sbar);
doublereal r = GasConstant;
scale(sbar, sbar+m_kk, sbar, r);
for (int k = 0; k < m_kk; k++) {
doublereal xx = fmaxx(SmallNumber, moleFraction(k));
sbar[k] += r * ( - log(xx));
}
}
void IdealGasPhase::getChemPotentials(doublereal* mu) const
{
getStandardChemPotentials(mu);
doublereal rt = temperature() * GasConstant;
for (size_t k = 0; k < m_kk; k++) {
double xx = std::max(SmallNumber, moleFraction(k));
mu[k] += rt * (log(xx));
}
}
doublereal MaskellSolidSolnPhase::entropy_mole() const
{
_updateThermo();
const doublereal s0 = GasConstant * mean_X(m_s0_R);
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));
}
doublereal Phase::moleFraction(const std::string& nameSpec) const
{
size_t iloc = speciesIndex(nameSpec);
if (iloc != npos) {
return moleFraction(iloc);
} else {
return 0.0;
}
}
void IdealSolnGasVPSS::getChemPotentials(doublereal* mu) const {
getStandardChemPotentials(mu);
doublereal xx;
doublereal rt = temperature() * GasConstant;
for (int k = 0; k < m_kk; k++) {
xx = fmaxx(SmallNumber, moleFraction(k));
mu[k] += rt*(log(xx));
}
}
/*
* Get the array of partial molar entropies of the species
* units = J / kmol / K
*/
void PecosGasPhase::getPartialMolarEntropies(doublereal* sbar) const {
const array_fp& _s = entropy_R_ref();
doublereal r = GasConstant;
scale(_s.begin(), _s.end(), sbar, r);
doublereal logp = log(pressure()/m_spthermo->refPressure());
for (int k = 0; k < m_kk; k++) {
doublereal xx = fmaxx(SmallNumber, moleFraction(k));
sbar[k] += r * (- logp - log(xx));
}
}
void LatticePhase::getChemPotentials(doublereal* mu) const
{
doublereal delta_p = m_Pcurrent - m_Pref;
const vector_fp& g_RT = gibbs_RT_ref();
for (size_t k = 0; k < m_kk; k++) {
double xx = std::max(SmallNumber, moleFraction(k));
mu[k] = RT() * (g_RT[k] + log(xx))
+ delta_p * m_speciesMolarVolume[k];
}
}
doublereal SurfPhase::entropy_mole() const
{
_updateThermo();
doublereal s = 0.0;
for (size_t k = 0; k < m_kk; k++) {
s += moleFraction(k) * (m_s0[k] -
GasConstant * log(std::max(concentration(k) * size(k)/m_n0, SmallNumber)));
}
return s;
}
doublereal Phase::chargeDensity() const
{
size_t kk = nSpecies();
doublereal cdens = 0.0;
for (size_t k = 0; k < kk; k++) {
cdens += charge(k)*moleFraction(k);
}
cdens *= Faraday;
return cdens;
}
void IdealGasPhase::getPartialMolarEntropies(doublereal* sbar) const
{
const vector_fp& _s = entropy_R_ref();
scale(_s.begin(), _s.end(), sbar, GasConstant);
doublereal logp = log(pressure() / m_spthermo->refPressure());
for (size_t k = 0; k < m_kk; k++) {
doublereal xx = std::max(SmallNumber, moleFraction(k));
sbar[k] += GasConstant * (-logp - log(xx));
}
}
void IdealSolidSolnPhase::getChemPotentials_RT(doublereal* mu) const
{
doublereal delta_pdRT = (m_Pcurrent - m_Pref) / (temperature() * GasConstant);
const vector_fp& g_RT = gibbs_RT_ref();
for (size_t k = 0; k < m_kk; k++) {
double xx = std::max(SmallNumber, moleFraction(k));
mu[k] = (g_RT[k] + log(xx))
+ delta_pdRT * m_speciesMolarVolume[k];
}
}
void PecosGasPhase::getChemPotentials(doublereal* mu) const {
getStandardChemPotentials(mu);
//doublereal logp = log(pressure()/m_spthermo->refPressure());
doublereal xx;
doublereal rt = temperature() * GasConstant;
//const array_fp& g_RT = gibbs_RT_ref();
for (int k = 0; k < m_kk; k++) {
xx = fmaxx(SmallNumber, moleFraction(k));
mu[k] += rt*(log(xx));
}
}
compositionMap Phase::getMoleFractionsByName(double threshold) const
{
compositionMap comp;
for (size_t k = 0; k < m_kk; k++) {
double x = moleFraction(k);
if (x > threshold) {
comp[speciesName(k)] = x;
}
}
return comp;
}
void ConstDensityThermo::getChemPotentials(doublereal* mu) const {
doublereal vdp = (pressure() - m_spthermo->refPressure())/
molarDensity();
doublereal xx;
doublereal rt = temperature() * GasConstant;
const array_fp& g_RT = gibbs_RT();
for (int k = 0; k < m_kk; k++) {
xx = fmaxx(SmallNumber, moleFraction(k));
mu[k] = rt*(g_RT[k] + log(xx)) + vdp;
}
}
void MaskellSolidSolnPhase::getChemPotentials(doublereal* mu) const
{
_updateThermo();
const doublereal r = moleFraction(product_species_index);
const doublereal pval = p(r);
const doublereal rfm = r * fm(r);
const doublereal DgbarDr = pval * h_mixing +
RT() *
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::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 rfm = r * fm(r);
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 IdealMolalSoln::getMolalityActivityCoefficients(doublereal* acMolality) const
{
if (IMS_typeCutoff_ == 0) {
for (size_t k = 0; k < m_kk; k++) {
acMolality[k] = 1.0;
}
double xmolSolvent = moleFraction(0);
// Limit the activity coefficient to be finite as the solvent mole
// fraction goes to zero.
xmolSolvent = std::max(m_xmolSolventMIN, xmolSolvent);
acMolality[0] = exp((xmolSolvent - 1.0)/xmolSolvent) / xmolSolvent;
} else {
s_updateIMS_lnMolalityActCoeff();
std::copy(IMS_lnActCoeffMolal_.begin(), IMS_lnActCoeffMolal_.end(), acMolality);
for (size_t k = 0; k < m_kk; k++) {
acMolality[k] = exp(acMolality[k]);
}
}
}