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);
}
}
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);
}
}
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;
}
}