documentation update
This commit is contained in:
Harry Moffat
parent
35819862c8
commit
aea7acd086
2 changed files with 156 additions and 84 deletions
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@ -987,6 +987,23 @@ private:
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*/
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int vcs_add_all_deleted();
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//! Recheck deleted species in multispecies phases.
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/*!
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* We are checking the equation:
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*
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* sum_u = sum_j_comp [ sigma_i_j * u_j ]
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* = u_i_O + log((AC_i * W_i)/m_tPhaseMoles_old)
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*
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* by first evaluating:
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*
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* DG_i_O = u_i_O - sum_u.
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*
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* Then, if TL is zero, the phase pops into existence if DG_i_O < 0.
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* Also, if the phase exists, then we check to see if the species
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* can have a mole number larger than VCS_DELETE_SPECIES_CUTOFF
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* (default value = 1.0E-32).
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*
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*/
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int recheck_deleted();
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//! Alternative treatment for the update of a minor species
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@ -2501,20 +2501,30 @@ namespace VCSnonideal {
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/*
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* Upload the state to the VP object
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*/
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Vphase->setMolesFromVCSCheck(VCS_DATA_PTR(m_molNumSpecies_old), VCS_DATA_PTR(m_tPhaseMoles_old), iph);
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} /* delete_multiphase() *****************************************************/
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Vphase->setMolesFromVCSCheck(VCS_DATA_PTR(m_molNumSpecies_old),
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VCS_DATA_PTR(m_tPhaseMoles_old), iph);
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}
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/************************************************************************************/
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/*****************************************************************************
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// Recheck deleted species in multispecies phases.
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/*
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* We are checking the equation:
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*
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* recheck_deleted:
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* sum_u = sum_j_comp [ sigma_i_j * u_j ]
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* = u_i_O + log((AC_i * W_i)/m_tPhaseMoles_old)
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*
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* Recheck deleted species in multispecies phases.
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* by first evaluating:
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*
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* DG_i_O = u_i_O - sum_u.
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*
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* Then, if TL is zero, the phase pops into existence if DG_i_O < 0.
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* Also, if the phase exists, then we check to see if the species
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* can have a mole number larger than VCS_DELETE_SPECIES_CUTOFF
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* (default value = 1.0E-32).
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*
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* HKM -> This algorithm needs to be updated for activity coefficients
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*/
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int VCS_SOLVE::recheck_deleted(void)
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{
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int VCS_SOLVE::recheck_deleted() {
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int iph, kspec, irxn, npb;
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double *xtcutoff = VCS_DATA_PTR(m_TmpPhase);
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#ifdef DEBUG_MODE
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@ -2526,11 +2536,16 @@ namespace VCSnonideal {
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/*
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* Use the standard chemical potentials for the chemical potentials
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* of deleted species. Then, calculate Delta G for
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* for formation reactions
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* for formation reactions.
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* Note: fe[] here includes everything except for the ln(x[i]) term
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*/
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for (kspec = m_numSpeciesRdc; kspec < m_numSpeciesTot; ++kspec) {
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m_feSpecies_curr[kspec] = m_SSfeSpecies[kspec];
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iph = m_phaseID[kspec];
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m_feSpecies_curr[kspec] = (m_SSfeSpecies[kspec] + log(m_actCoeffSpecies_old[kspec])
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- m_lnMnaughtSpecies[kspec]
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+ m_chargeSpecies[kspec] * m_Faraday_dim * m_phasePhi[iph]);
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}
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/*
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* Recalculate the DeltaG's of the formation reactions for the
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* deleted species in the mechanism
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@ -2543,6 +2558,7 @@ namespace VCSnonideal {
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else
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xtcutoff[iph] = 0.0;
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}
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/*
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*
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* We are checking the equation:
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@ -2552,7 +2568,7 @@ namespace VCSnonideal {
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*
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* by first evaluating:
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*
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* DG_i_O = u_i_O - sum_u.
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* DG_i_O = u_i_O - sum_u.
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*
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* Then, if TL is zero, the phase pops into existence if DG_i_O < 0.
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* Also, if the phase exists, then we check to see if the species
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@ -2566,7 +2582,7 @@ namespace VCSnonideal {
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*
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* sum_i_in_phase [ exp(-DG_i_O) ] >= 1.0
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*
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* Thus, we need to amend th code. Also nonideal solutions will tend to
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* Thus, we need to amend the code. Also nonideal solutions will tend to
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* complicate matters severely also.
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*/
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npb = 0;
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@ -2632,7 +2648,8 @@ namespace VCSnonideal {
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if (retn == 0) {
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#ifdef DEBUG_MODE
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if (m_debug_print_lvl) {
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plogf(" --- add_deleted(): delta_species() failed for species %s (%d) with mol number %g\n",
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plogf(" --- add_deleted(): delta_species() failed for "
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"species %s (%d) with mol number %g\n",
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m_speciesName[kspec].c_str(), kspec, dx);
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}
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#endif
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@ -2642,7 +2659,8 @@ namespace VCSnonideal {
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#ifdef DEBUG_MODE
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if (retn == 0) {
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if (m_debug_print_lvl) {
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plogf(" --- add_deleted(): delta_species() failed for species %s (%d) with mol number %g\n",
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plogf(" --- add_deleted(): delta_species() failed for "
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"species %s (%d) with mol number %g\n",
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m_speciesName[kspec].c_str(), kspec, dx);
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}
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}
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@ -4127,73 +4145,107 @@ namespace VCSnonideal {
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}
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return VCS_SPECIES_MINOR;
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}
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/*****************************************************************************/
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/*****************************************************************************/
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/*****************************************************************************/
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void VCS_SOLVE::vcs_chemPotPhase(int iph, const double *const molNum,
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//! We calculate the dimensionless chemical potentials of all species
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//! in a single phase.
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/*!
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*
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* We calculate the dimensionless chemical potentials of all species
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* in a single phase.
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*
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* Note, for multispecies phases which are currently zeroed out,
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* the chemical potential is filled out with the standard chemical
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* potential.
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*
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* For species in multispecies phases whose concentration is zero,
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* we need to set the mole fraction to a very low value.
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* It's chemical potential
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* is then calculated using the VCS_DELETE_MINORSPECIES_CUTOFF concentration
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* to keep numbers positive.
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*
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* Formula:
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* ---------------
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*
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* Ideal Mixtures:
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*
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* m_feSpecies(I) = m_SSfeSpecies(I) + ln(z(I)) - ln(m_tPhaseMoles[iph])
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* + m_chargeSpecies[I] * Faraday_dim * m_phasePhi[iphase];
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*
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*
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* ( This is equivalent to the adding the log of the
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* mole fraction onto the standard chemical
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* potential. )
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*
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* Non-Ideal Mixtures:
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* ActivityConvention = 0:
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*
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* m_feSpecies(I) = m_SSfeSpecies(I)
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* + ln(ActCoeff[I] * z(I)) - ln(m_tPhaseMoles[iph])
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* + m_chargeSpecies[I] * Faraday_dim * m_phasePhi[iphase];
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*
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* ( This is equivalent to the adding the log of the
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* mole fraction multiplied by the activity coefficient
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* onto the standard chemical potential. )
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*
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* ActivityConvention = 1: -> molality activity formulation
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*
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* m_feSpecies(I) = m_SSfeSpecies(I)
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* + ln(ActCoeff[I] * z(I)) - ln(m_tPhaseMoles[iph])
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* - ln(Mnaught * m_units)
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* + m_chargeSpecies[I] * Faraday_dim * m_phasePhi[iphase];
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*
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* note: m_SSfeSpecies(I) is the molality based standard state.
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* However, ActCoeff[I] is the molar based activity coefficient
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* We have used the formulas;
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*
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* ActCoeff_M[I] = ActCoeff[I] / Xmol[N]
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* where Xmol[N] is the mole fraction of the solvent
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* ActCoeff_M[I] is the molality based act coeff.
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*
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* note: This is equivalent to the "normal" molality formulation:
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*
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* m_feSpecies(I) = m_SSfeSpecies(I)
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* + ln(ActCoeff_M[I] * m(I))
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* + m_chargeSpecies[I] * Faraday_dim * m_phasePhi[iphase]
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* where m[I] is the molality of the ith solute
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*
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* m[I] = Xmol[I] / ( Xmol[N] * Mnaught * m_units)
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*
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*
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* note: z(I)/tPhMoles_ptr[iph] = Xmol[i] is the mole fraction
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* of i in the phase.
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*
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* NOTE:
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* As per the discussion in vcs_dfe(), for small species where the mole
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* fraction is small:
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*
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* z(i) < VCS_DELETE_MINORSPECIES_CUTOFF
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*
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* The chemical potential is calculated as:
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*
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* m_feSpecies(I) = m_SSfeSpecies(I)
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* + ln(ActCoeff[i](VCS_DELETE_MINORSPECIES_CUTOFF))
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*
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* Input
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* --------
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* @param iph Phase to be calculated
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* @param molNum molNum[i] is the number of moles of species i
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* (VCS species order)
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* @param do_deleted Do species that are deleted (default = false)
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*
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* Output
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* -----------
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* @param ac Activity coefficients for species in phase
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* (VCS species order)
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* @param mu_i Dimensionless chemical potentials for phase species
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* (VCS species order)
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*
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*/
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void VCS_SOLVE::vcs_chemPotPhase(const int iph, const double *const molNum,
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double * const ac, double * const mu_i,
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bool do_deleted)
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const bool do_deleted) {
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/**************************************************************************
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*
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* vcs_chemPotPhase:
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*
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* We calculate the dimensionless chemical potentials of all species
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* in a single phase.
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*
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* Formula:
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* ---------------
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*
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* Ideal Mixtures:
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*
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* fe(I) = ff(I) + ln(z(I)) - ln(tPhMoles_ptr[iph])
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*
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* ( This is equivalent to the adding the log of the
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* mole fraction onto the standard chemical
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* potential. )
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*
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* Non-Ideal Mixtures:
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* ActivityConvention = 0:
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* fe(I) = ff(I) + ln(ActCoeff[i]z(I)) - ln(tPhMoles_ptr[iph])
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*
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* ( This is equivalent to the adding the log of the
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* mole fraction multiplied by the activity coefficient
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* onto the standard chemical potential. )
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*
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* ActivityConvention = 1: -> molality activity formulation
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* fe(I) = ff(I) + ln(ActCoeff[i]z(I)) - ln(tPhMoles_ptr[iph])
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* - ln(Mnaught * m_units)
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*
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* note: z(I)/tPhMoles_ptr[iph] = Xmol[i] is the mole fraction
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* of i in the phase.
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*
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* NOTE:
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* As per the discussion in vcs_dfe(), for small species where the mole
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* fraction
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* z(i) < VCS_DELETE_MINORSPECIES_CUTOFF
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* The chemical potential is calculated as:
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* fe(I) = ff(I) + ln(ActCoeff[i](VCS_DELETE_MINORSPECIES_CUTOFF))
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*
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* Input
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* --------
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* iph : Phase to be calculated
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* molNum(i) : Number of moles of species i
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* (VCS species order)
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* ff : standard state chemical potentials. These are the
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* chemical potentials of the standard states at
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* the same T and P as the solution.
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* (VCS species order)
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* Output
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* -------
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* ac[] : Activity coefficients for species in phase
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* (VCS species order)
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* mu_i[] : Dimensionless chemical potentials for phase species
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* (VCS species order)
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*
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*************************************************************************/
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{
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vcs_VolPhase *Vphase = m_VolPhaseList[iph];
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int nkk = Vphase->NVolSpecies;
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int k, kspec;
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@ -4254,7 +4306,7 @@ namespace VCSnonideal {
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}
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}
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}
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/*****************************************************************************/
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/*********************************************************************************/
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// Calculalte the dimensionless chemical potentials of all species or
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// of certain groups of species, at a fixed temperature and pressure.
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@ -4316,11 +4368,14 @@ namespace VCSnonideal {
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* where Xmol[N] is the mole fraction of the solvent
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* ActCoeff_M[I] is the molality based act coeff.
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*
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* m_feSpecies(I) = m_SSfeSpecies(I)
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* + ln(ActCoeff_M[I] * m(I))
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* + m_chargeSpecies[I] * Faraday_dim * m_phasePhi[iphase]
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* where m[I] is the molality of the ith solute
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*
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* note: This is equivalent to the "normal" molality formulation below:
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*
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* m_feSpecies(I) = m_SSfeSpecies(I)
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* + ln(ActCoeff_M[I] * m(I))
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* + m_chargeSpecies[I] * Faraday_dim * m_phasePhi[iphase]
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* where m[I] is the molality of the ith solute
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*
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*
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* m[I] = Xmol[I] / ( Xmol[N] * Mnaught * m_units)
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*
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*
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