TEST(HMWSoln, fromScratch)
{
// Regression test based on HMW_test_3
HMWSoln p;
auto sH2O = make_species("H2O(l)", "H:2, O:1", h2oliq_nasa_coeffs);
auto sCl = make_species("Cl-", "Cl:1, E:1", 0.0,
298.15, -52.8716, 333.15, -52.8716, 1e5);
sCl->charge = -1;
auto sH = make_species("H+", "H:1, E:-1", 0.0, 298.15, 0.0, 333.15, 0.0, 1e5);
sH->charge = 1;
auto sNa = make_species("Na+", "Na:1, E:-1", 0.0,
298.15, -125.5213, 333.15, -125.5213, 1e5);
sNa->charge = 1;
auto sOH = make_species("OH-", "O:1, H:1, E:1", 0.0,
298.15, -91.523, 333.15, -91.523, 1e5);
sOH->charge = -1;
for (auto& s : {sH2O, sCl, sH, sNa, sOH}) {
p.addSpecies(s);
}
std::unique_ptr<PDSS_Water> ss(new PDSS_Water());
p.installPDSS(0, std::move(ss));
size_t k = 1;
for (double v : {1.3, 1.3, 1.3, 1.3}) {
std::unique_ptr<PDSS_ConstVol> ss(new PDSS_ConstVol());
ss->setMolarVolume(v);
p.installPDSS(k++, std::move(ss));
}
p.setPitzerTempModel("complex");
p.setA_Debye(1.175930);
p.initThermo();
set_hmw_interactions(p);
p.setMolalitiesByName("Na+:6.0997 Cl-:6.0996986044628 H+:2.1628E-9 OH-:1.3977E-6");
p.setState_TP(150 + 273.15, 101325);
size_t N = p.nSpecies();
vector_fp acMol(N), mf(N), activities(N), moll(N), mu0(N);
p.getMolalityActivityCoefficients(acMol.data());
p.getMoleFractions(mf.data());
p.getActivities(activities.data());
p.getMolalities(moll.data());
p.getStandardChemPotentials(mu0.data());
double acMolRef[] = {0.9341, 1.0191, 3.9637, 1.0191, 0.4660};
double mfRef[] = {0.8198, 0.0901, 0.0000, 0.0901, 0.0000};
double activitiesRef[] = {0.7658, 6.2164, 0.0000, 6.2164, 0.0000};
double mollRef[] = {55.5084, 6.0997, 0.0000, 6.0997, 0.0000};
double mu0Ref[] = {-317.175788, -186.014558, 0.0017225, -441.615429, -322.000412}; // kJ/gmol
for (size_t k = 0 ; k < N; k++) {
EXPECT_NEAR(acMol[k], acMolRef[k], 2e-4);
EXPECT_NEAR(mf[k], mfRef[k], 2e-4);
EXPECT_NEAR(activities[k], activitiesRef[k], 2e-4);
EXPECT_NEAR(moll[k], mollRef[k], 2e-4);
EXPECT_NEAR(mu0[k]/1e6, mu0Ref[k], 2e-6);
}
}
int main(int argc, char** argv)
{
int retn = 0;
size_t i;
try {
std::string iFile = (argc > 1) ? argv[1] : "HMW_NaCl.xml";
double V0[20], pmV[20];
HMWSoln* HMW = new HMWSoln(iFile, "NaCl_electrolyte");
/*
* Load in and initialize the
*/
Cantera::thermo_t* solid = newPhase<doublereal>("NaCl_Solid.xml","NaCl(S)");
size_t nsp = HMW->nSpecies();
//double acMol[100];
//double act[100];
double mf[100];
double moll[100];
HMW->getMoleFractions(mf);
string sName;
TemperatureTable TTable(15, false, 273.15, 25., 0, 0);
HMW->setState_TP(298.15, 1.01325E5);
size_t i1 = HMW->speciesIndex("Na+");
size_t i2 = HMW->speciesIndex("Cl-");
//int i3 = HMW->speciesIndex("H2O(L)");
for (i = 0; i < nsp; i++) {
moll[i] = 0.0;
}
HMW->setMolalities(moll);
/*
* Set the Pressure
*/
double pres = OneAtm;
/*
* Fix the molality
*/
double Is = 6.146;
moll[i1] = Is;
moll[i2] = Is;
HMW->setState_TPM(298.15, pres, moll);
double Xmol[30];
HMW->getMoleFractions(Xmol);
double meanMW = HMW->meanMolecularWeight();
/*
* ThermoUnknowns
*/
double T;
double V0_NaCl = 0.0, V0_Naplus = 0.0, V0_Clminus = 0.0, Delta_V0s = 0.0, V0_H2O = 0.0;
double V_NaCl = 0.0, V_Naplus = 0.0, V_Clminus = 0.0, V_H2O = 0.0;
double molarV0;
#ifdef DEBUG_HKM
FILE* ttt = fopen("table.csv","w");
#endif
printf("A_V : Comparison to Pitzer's book, p. 99, can be made.\n");
printf(" Agreement to 3 sig digits \n");
printf("\n");
printf("Delta_V0: Heat Capacity of Solution per mole of salt (standard states)\n");
printf(" rxn for the ss heat of soln: "
"NaCl(s) -> Na+(aq) + Cl-(aq)\n");
printf("\n");
printf("Delta_Vs: Delta volume of Solution per mole of salt\n");
printf(" rxn for heat of soln: "
" n1 H2O(l,pure) + n2 NaCl(s) -> n2 MX(aq) + n1 H2O(l) \n");
printf(" Delta_Hs = (n1 h_H2O_bar + n2 h_MX_bar "
"- n1 h_H2O_0 - n2 h_MX_0)/n2\n");
printf("\n");
printf("phiV: phiV, calculated from the program, is checked\n");
printf(" against analytical formula in V_standalone program.\n");
printf(" (comparison against Pitzer book, p. 97, eqn. 96)\n");
/*
* Create a Table of NaCl Enthalpy Properties as a Function
* of the Temperature
*/
printf("\n\n");
printf(" T, Pres, Aphi, A_V,"
" Delta_V0,"
" Delta_Vs, Vex, phiV,"
" MolarV, MolarV0\n");
printf(" Kelvin, bar, sqrt(kg/gmol),sqrt(kg/gmol)cm3/gmol,"
"cm**3/gmolSalt,"
"cm**3/gmolSalt,cm**3/gmolSoln,cm**3/gmolSalt,"
"cm**3/gmol, cm**3/gmol\n");
#ifdef DEBUG_HKM
fprintf(ttt,"T, Pres, A_V, Vex, phiV, MolarV, MolarV0\n");
fprintf(ttt,"Kelvin, bar, sqrt(kg/gmol)cm3/gmol, cm3/gmolSoln, cm3/gmolSalt, kJ/gmolSoln,"
"kJ/gmolSoln\n");
#endif
for (i = 0; i < TTable.NPoints + 1; i++) {
if (i == TTable.NPoints) {
T = 323.15;
} else {
T = TTable.T[i];
}
/*
* RT is in units of J/kmolK
*/
//double RT = GasConstant * T;
/*
* Make sure we are at the saturation pressure or above.
*/
double psat = HMW->satPressure(T);
pres = OneAtm;
if (psat > pres) {
pres = psat;
}
HMW->setState_TPM(T, pres, moll);
solid->setState_TP(T, pres);
/*
* Get the Standard State volumes m3/kmol
*/
solid->getStandardVolumes(V0);
V0_NaCl = V0[0];
HMW->getStandardVolumes(V0);
V0_H2O = V0[0];
V0_Naplus = V0[i1];
V0_Clminus = V0[i2];
/*
* Calculate the standard state volume change of solution
* for NaCl(s) -> Na+ + Cl-
* units: m3 / kmol
*/
Delta_V0s = V0_Naplus + V0_Clminus - V0_NaCl;
double dd = solid->density();
double MW_NaCl = solid->meanMolecularWeight();
V_NaCl = MW_NaCl / dd;
//printf("V_NaCl = %g , V0_NaCl = %g %g\n", V_NaCl, V0_NaCl, 1.0/solid->molarDensity());
/*
* Get the partial molar volumes
*/
HMW->getPartialMolarVolumes(pmV);
V_H2O = pmV[0];
V_Naplus = pmV[i1];
V_Clminus = pmV[i2];
//double Delta_V_Salt = V_NaCl - (V_Naplus + V_Clminus);
/*
* Calculate the molar volume of solution
*/
double dsoln = HMW->density();
meanMW = HMW->meanMolecularWeight();
double molarV = meanMW / dsoln;
//double md = HMW->molarDensity();
//printf("compare %g %g\n", molarV, 1.0/md);
/*
* Calculate the delta volume of solution for the reaction
* NaCl(s) -> Na+ + Cl-
*/
double Delta_Vs = (Xmol[0] * V_H2O +
Xmol[i1] * V_Naplus +
Xmol[i2] * V_Clminus
- Xmol[0] * V0_H2O
- Xmol[i1] * V_NaCl);
Delta_Vs /= Xmol[i1];
/*
* Calculate the apparent molar volume, J, from the
* partial molar quantities, units m3/kmol
*/
double Vex = (Xmol[0] * (V_H2O - V0_H2O) +
Xmol[i1] * (V_Naplus - V0_Naplus) +
Xmol[i2] * (V_Clminus - V0_Clminus));
/*
* Calculate the apparent relative molal volume, phiV,
* units of m3/kmol
*/
double phiV = Vex / Xmol[i1];
double Aphi = HMW->A_Debye_TP(T, pres) / 3.0;
//double AL = HMW->ADebye_L(T,pres);
double Av = HMW->ADebye_V(T, pres) * 1.0E3;
molarV0 = 0.0;
for (size_t k = 0; k < nsp; k++) {
molarV0 += Xmol[k] * V0[k];
}
if (i != TTable.NPoints+1) {
printf("%13.4g, %13.4g, %13.4g, %13.4g, %13.4g, %13.4g, "
"%13.5g, %13.4g, %13.4g, %13.4g\n",
T, pres*1.0E-5, Aphi, Av, Delta_V0s*1.0E3, Delta_Vs*1.0E3,
Vex*1.0E3, phiV*1.0E3, molarV*1.0E3 , molarV0*1.0E3);
#ifdef DEBUG_HKM
fprintf(ttt,"%g, %g, %g, %g, %g, %g, %g\n",
T, pres*1.0E-5, Av, Vex*1.0E3, phiV*1.0E3, molarV*1.0E3 , molarV0*1.0E3);
#endif
}
}
printf("Breakdown of Volume Calculation at 323.15 K, 1atm:\n");
printf(" Species MoleFrac Molal V0 "
" partV (partV - V0)\n");
printf(" H2O(L)");
printf("%13.4g %13.4g %13.4g %13.4g %13.4g\n", Xmol[0], moll[0], V0_H2O*1.E3, V_H2O*1.E3,
(V_H2O-V0_H2O)*1.E3);
printf(" Na+ ");
printf("%13.4g %13.4g %13.4g %13.4g %13.4g\n", Xmol[i1], moll[i1],
V0_Naplus*1.E3 , V_Naplus*1.E3, (V_Naplus -V0_Naplus)*1.E3);
printf(" Cl- ");
printf("%13.4g %13.4g %13.4g %13.4g %13.4g\n", Xmol[i2], moll[i2],
V0_Clminus*1.E3, V_Clminus*1.E3, (V_Clminus - V0_Clminus)*1.E3);
printf(" NaCl(s)");
double dd = V_NaCl*1.E3 - V0_NaCl*1.E3;
if (fabs(dd) < 1.0E-12) {
dd = 0.0;
}
printf("%13.4g %13.4g %13.4g %13.4g\n", 1.0,
V0_NaCl*1.E3 , V_NaCl*1.E3, dd);
delete HMW;
HMW = 0;
delete solid;
solid = 0;
Cantera::appdelete();
#ifdef DEBUG_HKM
fclose(ttt);
#endif
return retn;
} catch (CanteraError& err) {
std::cout << err.what() << std::endl;
Cantera::appdelete();
return -1;
}
}
int main(int argc, char** argv)
{
int retn = 0;
size_t i;
try {
std::string iFile = (argc > 1) ? argv[1] : "HMW_NaCl.xml";
double Cp0_R[20], pmCp[20];
HMWSoln* HMW = new HMWSoln(iFile, "NaCl_electrolyte");
/*
* Load in and initialize the
*/
Cantera::thermo_t* solid = newPhase<doublereal>("NaCl_Solid.xml","NaCl(S)");
size_t nsp = HMW->nSpecies();
double mf[100];
double moll[100];
for (i = 0; i < 100; i++) {
mf[i] = 0.0;
}
HMW->getMoleFractions(mf);
string sName;
TemperatureTable TTable(15, false, 273.15, 25., 0, 0);
HMW->setState_TP(298.15, 1.01325E5);
size_t i1 = HMW->speciesIndex("Na+");
size_t i2 = HMW->speciesIndex("Cl-");
//int i3 = HMW->speciesIndex("H2O(L)");
for (i = 0; i < nsp; i++) {
moll[i] = 0.0;
}
HMW->setMolalities(moll);
double Is = 0.0;
/*
* Set the Pressure
*/
double pres = OneAtm;
/*
* Fix the molality
*/
Is = 6.146;
moll[i1] = Is;
moll[i2] = Is;
HMW->setState_TPM(298.15, pres, moll);
double Xmol[30];
HMW->getMoleFractions(Xmol);
/*
* ThermoUnknowns
*/
double T;
double Cp0_NaCl = 0.0, Cp0_Naplus = 0.0, Cp0_Clminus = 0.0, Delta_Cp0s = 0.0, Cp0_H2O = 0.0;
double Cp_NaCl = 0.0, Cp_Naplus = 0.0, Cp_Clminus = 0.0, Cp_H2O = 0.0;
double molarCp0;
#ifdef DEBUG_HKM
FILE* ttt = fopen("table.csv","w");
#endif
printf("A_J/R: Comparison to Pitzer's book, p. 99, can be made.\n");
printf(" Agreement is within 12 pc \n");
printf("\n");
printf("Delta_Cp0: Heat Capacity of Solution per mole of salt (standard states)\n");
printf(" rxn for the ss heat of soln: "
"NaCl(s) -> Na+(aq) + Cl-(aq)\n");
printf("\n");
printf("Delta_Cps: Delta heat Capacity of Solution per mole of salt\n");
printf(" rxn for heat of soln: "
" n1 H2O(l,pure) + n2 NaCl(s) -> n2 MX(aq) + n1 H2O(l) \n");
printf(" Delta_Hs = (n1 h_H2O_bar + n2 h_MX_bar "
"- n1 h_H2O_0 - n2 h_MX_0)/n2\n");
printf("\n");
printf("phiJ: phiJ, calculated from the program, is checked\n");
printf(" against analytical formula in J_standalone program.\n");
printf(" (comparison against Eq. 12, Silvester and Pitzer)\n");
/*
* Create a Table of NaCl Enthalpy Properties as a Function
* of the Temperature
*/
printf("\n\n");
printf(" T, Pres, Aphi, A_J/R,"
" Delta_Cp0,"
" Delta_Cps, J, phiJ,"
" MolarCp, MolarCp0\n");
printf(" Kelvin, bar, sqrt(kg/gmol), sqrt(kg/gmol),"
" kJ/gmolSalt,"
" kJ/gmolSalt, kJ/gmolSoln, kJ/gmolSalt,"
" kJ/gmol, kJ/gmol\n");
#ifdef DEBUG_HKM
fprintf(ttt,"T, Pres, A_J/R, Delta_Cp0, Delta_Cps, J, phiJ\n");
fprintf(ttt,"Kelvin, bar, sqrt(kg/gmol), kJ/gmolSalt, kJ/gmolSalt, kJ/gmolSoln,"
"kJ/gmolSalt\n");
#endif
for (i = 0; i < TTable.NPoints + 1; i++) {
if (i == TTable.NPoints) {
T = 323.15;
} else {
T = TTable.T[i];
}
/*
* RT is in units of J/kmolK
*/
//double RT = GasConstant * T;
/*
* Make sure we are at the saturation pressure or above.
*/
double psat = HMW->satPressure(T);
pres = OneAtm;
if (psat > pres) {
pres = psat;
}
HMW->setState_TPM(T, pres, moll);
solid->setState_TP(T, pres);
/*
* Get the Standard State DeltaH
*/
solid->getCp_R(Cp0_R);
Cp0_NaCl = Cp0_R[0] * GasConstant * 1.0E-6;
HMW->getCp_R(Cp0_R);
Cp0_H2O = Cp0_R[0] * GasConstant * 1.0E-6;
Cp0_Naplus = Cp0_R[i1] * GasConstant * 1.0E-6;
Cp0_Clminus = Cp0_R[i2] * GasConstant * 1.0E-6;
/*
* Calculate the standard state heat of solution
* for NaCl(s) -> Na+ + Cl-
* units: kJ/gmolSalt
*/
Delta_Cp0s = Cp0_Naplus + Cp0_Clminus - Cp0_NaCl;
pmCp[0] = solid->cp_mole();
Cp_NaCl = pmCp[0] * 1.0E-6;
HMW->getPartialMolarCp(pmCp);
Cp_H2O = pmCp[0] * 1.0E-6;
Cp_Naplus = pmCp[i1] * 1.0E-6;
Cp_Clminus = pmCp[i2] * 1.0E-6;
//double Delta_Cp_Salt = Cp_NaCl - (Cp_Naplus + Cp_Clminus);
double molarCp = HMW->cp_mole() * 1.0E-6;
/*
* Calculate the heat capacity of solution for the reaction
* NaCl(s) -> Na+ + Cl-
*/
double Delta_Cps = (Xmol[0] * Cp_H2O +
Xmol[i1] * Cp_Naplus +
Xmol[i2] * Cp_Clminus
- Xmol[0] * Cp0_H2O
- Xmol[i1] * Cp_NaCl);
Delta_Cps /= Xmol[i1];
/*
* Calculate the relative heat capacity, J, from the
* partial molar quantities, units J/gmolSolutionK
*/
double J = (Xmol[0] * (Cp_H2O - Cp0_H2O) +
Xmol[i1] * (Cp_Naplus - Cp0_Naplus) +
Xmol[i2] * (Cp_Clminus - Cp0_Clminus));
/*
* Calculate the apparent relative molal heat capacity, phiJ,
* units of J/gmolSaltAddedK
*/
double phiJ = J / Xmol[i1];
double Aphi = HMW->A_Debye_TP(T, pres) / 3.0;
//double AL = HMW->ADebye_L(T,pres);
double AJ = HMW->ADebye_J(T, pres);
for (size_t k = 0; k < nsp; k++) {
Cp0_R[k] *= GasConstant * 1.0E-6;
}
molarCp0 = 0.0;
for (size_t k = 0; k < nsp; k++) {
molarCp0 += Xmol[k] * Cp0_R[k];
}
if (i != TTable.NPoints+1) {
printf("%13.5g, %13.5g, %13.5g, %13.5g, %13.5g, %13.5g, "
"%13.5g, %13.5g, %13.5g, %13.5g\n",
T, pres*1.0E-5, Aphi, AJ/GasConstant, Delta_Cp0s, Delta_Cps,
J, phiJ, molarCp , molarCp0);
#ifdef DEBUG_HKM
fprintf(ttt,"%g, %g, %g, %g, %g, %g, %g\n",
T, pres*1.0E-5, AJ/GasConstant, Delta_Cp0s, Delta_Cps, J, phiJ);
#endif
}
}
printf("Breakdown of Heat Capacity Calculation at 323.15 K, 1atm:\n");
printf(" Species MoleFrac Molal Cp0 "
" partCp (partCp - Cp0)\n");
printf(" H2O(L)");
printf("%13.5g %13.5g %13.5g %13.5g %13.5g\n", Xmol[0], moll[0], Cp0_H2O , Cp_H2O, Cp_H2O-Cp0_H2O);
printf(" Na+ ");
printf("%13.5g %13.5g %13.5g %13.5g %13.5g\n", Xmol[i1], moll[i1],
Cp0_Naplus , Cp_Naplus, Cp_Naplus -Cp0_Naplus);
printf(" Cl- ");
printf("%13.5g %13.5g %13.5g %13.5g %13.5g\n", Xmol[i2], moll[i2],
Cp0_Clminus , Cp_Clminus, Cp_Clminus - Cp0_Clminus);
printf(" NaCl(s)");
printf("%13.5g %13.5g %13.5g %13.5g\n", 1.0,
Cp0_NaCl , Cp_NaCl, Cp_NaCl - Cp0_NaCl);
delete HMW;
HMW = 0;
delete solid;
solid = 0;
Cantera::appdelete();
#ifdef DEBUG_HKM
fclose(ttt);
#endif
return retn;
} catch (CanteraError& err) {
std::cout << err.what() << std::endl;
Cantera::appdelete();
return -1;
}
}
int main(int argc, char** argv)
{
int retn = 0;
size_t i;
string commandFile;
try {
char iFile[80];
strcpy(iFile, "HMW_NaCl.xml");
if (argc > 1) {
strcpy(iFile, argv[1]);
}
double Temp = 273.15 + 275.;
double aTemp[7];
aTemp[0] = 298.15;
aTemp[1] = 273.15 + 100.;
aTemp[2] = 273.15 + 150.;
aTemp[3] = 273.15 + 200.;
aTemp[4] = 273.15 + 250.;
aTemp[5] = 273.15 + 275.;
aTemp[6] = 273.15 + 300.;
HMWSoln* HMW = new HMWSoln(iFile, "NaCl_electrolyte");
size_t nsp = HMW->nSpecies();
double acMol[100];
double act[100];
double mf[100];
double moll[100];
for (i = 0; i < 100; i++) {
acMol[i] = 1.0;
act[i] = 1.0;
mf[i] = 0.0;
moll[i] = 0.0;
}
HMW->getMoleFractions(mf);
string sName;
FILE* ff;
char fname[64];
for (int jTemp = 0; jTemp < 7; jTemp++) {
Temp = aTemp[jTemp];
sprintf(fname, "T%3.0f.csv", Temp);
ff = fopen(fname, "w");
HMW->setState_TP(Temp, 1.01325E5);
printf(" Temperature = %g K\n", Temp);
size_t i1 = HMW->speciesIndex("Na+");
size_t i2 = HMW->speciesIndex("Cl-");
size_t i3 = HMW->speciesIndex("H2O(L)");
for (i = 1; i < nsp; i++) {
moll[i] = 0.0;
}
HMW->setState_TPM(Temp, OneAtm, moll);
double Itop = 10.;
double Ibot = 0.0;
double ISQRTtop = sqrt(Itop);
double ISQRTbot = sqrt(Ibot);
double ISQRT;
double Is = 0.0;
size_t its = 100;
bool doneSp = false;
fprintf(ff," Is, sqrtIs, meanAc,"
" log10(meanAC), acMol_Na+,"
" acMol_Cl-, ac_Water, act_Water, OsmoticCoeff\n");
for (i = 0; i < its; i++) {
ISQRT = ISQRTtop*((double)i)/(its - 1.0)
+ ISQRTbot*(1.0 - (double)i/(its - 1.0));
Is = ISQRT * ISQRT;
if (!doneSp) {
if (Is > 6.146) {
Is = 6.146;
doneSp = true;
i = i - 1;
}
}
moll[i1] = Is;
moll[i2] = Is;
HMW->setMolalities(moll);
HMW->getMolalityActivityCoefficients(acMol);
HMW->getActivities(act);
double oc = HMW->osmoticCoefficient();
double meanAC = sqrt(acMol[i1] * acMol[i2]);
fprintf(ff,"%15g, %15g, %15g, %15g, %15g, %15g, %15g, %15g, %15g\n",
Is, ISQRT, meanAC, log10(meanAC),
acMol[i1], acMol[i2], acMol[i3], act[i3], oc);
}
fclose(ff);
}
delete HMW;
HMW = 0;
Cantera::appdelete();
return retn;
} catch (CanteraError& err) {
std::cout << err.what() << std::endl;
return -1;
}
}