void ThermoPhase::getdlnActCoeffdlnN_numderiv(const size_t ld, doublereal* const dlnActCoeffdlnN)
{
double deltaMoles_j = 0.0;
double pres = pressure();
// Evaluate the current base activity coefficients if necessary
vector_fp ActCoeff_Base(m_kk);
getActivityCoefficients(ActCoeff_Base.data());
vector_fp Xmol_Base(m_kk);
getMoleFractions(Xmol_Base.data());
// Make copies of ActCoeff and Xmol_ for use in taking differences
vector_fp ActCoeff(m_kk);
vector_fp Xmol(m_kk);
double v_totalMoles = 1.0;
double TMoles_base = v_totalMoles;
// Loop over the columns species to be deltad
for (size_t j = 0; j < m_kk; j++) {
// Calculate a value for the delta moles of species j
// -> Note Xmol_[] and Tmoles are always positive or zero quantities.
// -> experience has shown that you always need to make the deltas
// greater than needed to change the other mole fractions in order
// to capture some effects.
double moles_j_base = v_totalMoles * Xmol_Base[j];
deltaMoles_j = 1.0E-7 * moles_j_base + v_totalMoles * 1.0E-13 + 1.0E-150;
// Now, update the total moles in the phase and all of the mole
// fractions based on this.
v_totalMoles = TMoles_base + deltaMoles_j;
for (size_t k = 0; k < m_kk; k++) {
Xmol[k] = Xmol_Base[k] * TMoles_base / v_totalMoles;
}
Xmol[j] = (moles_j_base + deltaMoles_j) / v_totalMoles;
// Go get new values for the activity coefficients.
// -> Note this calls setState_PX();
setState_PX(pres, Xmol.data());
getActivityCoefficients(ActCoeff.data());
// Calculate the column of the matrix
double* const lnActCoeffCol = dlnActCoeffdlnN + ld * j;
for (size_t k = 0; k < m_kk; k++) {
lnActCoeffCol[k] = (2*moles_j_base + deltaMoles_j) *(ActCoeff[k] - ActCoeff_Base[k]) /
((ActCoeff[k] + ActCoeff_Base[k]) * deltaMoles_j);
}
// Revert to the base case Xmol_, v_totalMoles
v_totalMoles = TMoles_base;
Xmol = Xmol_Base;
}
setState_PX(pres, Xmol_Base.data());
}
void IdealGasPhase::setToEquilState(const doublereal* mu_RT)
{
const vector_fp& grt = gibbs_RT_ref();
/*
* Within the method, we protect against inf results if the
* exponent is too high.
*
* If it is too low, we set
* the partial pressure to zero. This capability is needed
* by the elemental potential method.
*/
doublereal pres = 0.0;
for (size_t k = 0; k < m_kk; k++) {
double tmp = -grt[k] + mu_RT[k];
if (tmp < -600.) {
m_pp[k] = 0.0;
} else if (tmp > 300.0) {
double tmp2 = tmp / 300.;
tmp2 *= tmp2;
m_pp[k] = m_p0 * exp(300.) * tmp2;
} else {
m_pp[k] = m_p0 * exp(tmp);
}
pres += m_pp[k];
}
// set state
setState_PX(pres, &m_pp[0]);
}
void IdealSolnGasVPSS::setToEquilState(const doublereal* mu_RT)
{
double tmp, tmp2;
updateStandardStateThermo();
const array_fp& grt = m_VPSS_ptr->Gibbs_RT_ref();
/*
* Within the method, we protect against inf results if the
* exponent is too high.
*
* If it is too low, we set
* the partial pressure to zero. This capability is needed
* by the elemental potential method.
*/
doublereal pres = 0.0;
double m_p0 = m_VPSS_ptr->refPressure();
for (int k = 0; k < m_kk; k++) {
tmp = -grt[k] + mu_RT[k];
if (tmp < -600.) {
m_pp[k] = 0.0;
} else if (tmp > 500.0) {
tmp2 = tmp / 500.;
tmp2 *= tmp2;
m_pp[k] = m_p0 * exp(500.) * tmp2;
} else {
m_pp[k] = m_p0 * exp(tmp);
}
pres += m_pp[k];
}
// set state
setState_PX(pres, &m_pp[0]);
}
void IdealSolidSolnPhase::setToEquilState(const doublereal* lambda_RT)
{
const vector_fp& grt = gibbs_RT_ref();
// set the pressure and composition to be consistent with
// the temperature,
doublereal pres = 0.0;
for (size_t k = 0; k < m_kk; k++) {
m_pp[k] = -grt[k];
for (size_t m = 0; m < nElements(); m++) {
m_pp[k] += nAtoms(k,m)*lambda_RT[m];
}
m_pp[k] = m_Pref * exp(m_pp[k]);
pres += m_pp[k];
}
setState_PX(pres, &m_pp[0]);
}
