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;
}
}
TEST(HMWSoln, fromScratch_HKFT)
{
HMWSoln p;
auto sH2O = make_species("H2O(l)", "H:2, O:1", h2oliq_nasa_coeffs);
auto sNa = make_species("Na+", "Na:1, E:-1", 0.0,
298.15, -125.5213, 333.15, -125.5213, 1e5);
sNa->charge = 1;
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 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, sNa, sCl, sH, sOH}) {
p.addSpecies(s);
}
double h0[] = {-57433, Undef, 0.0, -54977};
double g0[] = {Undef, -31379, 0.0, -37595};
double s0[] = {13.96, 13.56, Undef, -2.56};
double a[][4] = {{0.1839, -228.5, 3.256, -27260},
{0.4032, 480.1, 5.563, -28470},
{0.0, 0.0, 0.0, 0.0},
{0.12527, 7.38, 1.8423, -27821}};
double c[][2] = {{18.18, -29810}, {-4.4, -57140}, {0.0, 0.0}, {4.15, -103460}};
double omega[] = {33060, 145600, 0.0, 172460};
std::unique_ptr<PDSS_Water> ss(new PDSS_Water());
p.installPDSS(0, std::move(ss));
for (size_t k = 0; k < 4; k++) {
std::unique_ptr<PDSS_HKFT> ss(new PDSS_HKFT());
if (h0[k] != Undef) {
ss->setDeltaH0(h0[k] * toSI("cal/gmol"));
}
if (g0[k] != Undef) {
ss->setDeltaG0(g0[k] * toSI("cal/gmol"));
}
if (s0[k] != Undef) {
ss->setS0(s0[k] * toSI("cal/gmol/K"));
}
a[k][0] *= toSI("cal/gmol/bar");
a[k][1] *= toSI("cal/gmol");
a[k][2] *= toSI("cal-K/gmol/bar");
a[k][3] *= toSI("cal-K/gmol");
c[k][0] *= toSI("cal/gmol/K");
c[k][1] *= toSI("cal-K/gmol");
ss->set_a(a[k]);
ss->set_c(c[k]);
ss->setOmega(omega[k] * toSI("cal/gmol"));
p.installPDSS(k+1, std::move(ss));
}
p.setPitzerTempModel("complex");
p.setA_Debye(-1);
p.initThermo();
set_hmw_interactions(p);
p.setMolalitiesByName("Na+:6.0954 Cl-:6.0954 H+:2.1628E-9 OH-:1.3977E-6");
p.setState_TP(50 + 273.15, 101325);
size_t N = p.nSpecies();
vector_fp mv(N), h(N), mu(N), ac(N), acoeff(N);
p.getPartialMolarVolumes(mv.data());
p.getPartialMolarEnthalpies(h.data());
p.getChemPotentials(mu.data());
p.getActivities(ac.data());
p.getActivityCoefficients(acoeff.data());
double mvRef[] = {0.01815224, 0.00157182, 0.01954605, 0.00173137, -0.0020266};
for (size_t k = 0; k < N; k++) {
EXPECT_NEAR(mv[k], mvRef[k], 2e-8);
}
}