int main(int argc, char** argv)
{
#if defined(_MSC_VER) && _MSC_VER < 1900
_set_output_format(_TWO_DIGIT_EXPONENT);
#endif
int retn = 0;
try {
HMWSoln* HMW = new HMWSoln("HMW_NaCl.xml");
HMW->printCoeffs();
size_t nsp = HMW->nSpecies();
double a1 = HMW->AionicRadius(1);
printf("a1 = %g\n", a1);
double a2 = HMW->AionicRadius(2);
printf("a2 = %g\n", a2);
double mu0[100];
double moll[100];
string sName;
HMW->getMolalities(moll);
moll[1] = 6.0997;
moll[2] = 2.1628E-9;
moll[3] = 6.0997;
moll[4] =1.3977E-6;
/*
* Equalize charge balance and dump into Cl-
*/
double sum = -moll[1] + moll[2] + moll[3] - moll[4];
moll[1] += sum;
HMW->setMolalities(moll);
HMW->setState_TP(298.15, 1.01325E5);
pAtable(HMW);
HMW->setState_TP(298.15, 1.01325E5);
HMW->getStandardChemPotentials(mu0);
// translate from J/kmol to kJ/gmol
for (size_t k = 0; k < nsp; k++) {
mu0[k] *= 1.0E-6;
}
printf(" Species Standard chemical potentials (kJ/gmol) \n");
printf("------------------------------------------------------------\n");
for (size_t k = 0; k < nsp; k++) {
sName = HMW->speciesName(k);
printf("%16s %16.9g\n", sName.c_str(), mu0[k]);
}
printf("------------------------------------------------------------\n");
printf(" Some DeltaSS values: Delta(mu_0)\n");
double deltaG;
size_t i1, i2, j1;
double RT = 8.314472E-3 * 298.15;
i1 = HMW->speciesIndex("Na+");
i2 = HMW->speciesIndex("Cl-");
deltaG = -432.6304 - mu0[i1] - mu0[i2];
printf(" NaCl(S): Na+ + Cl- -> NaCl(S): %14.7g kJ/gmol \n",
deltaG);
printf(" : %14.7g (dimensionless) \n",
deltaG/RT);
printf(" : %14.7g (dimensionless/ln10) \n",
deltaG/(RT * log(10.0)));
printf(" G0(NaCl(S)) = %14.7g (fixed)\n", -432.6304);
printf(" G0(Na+) = %14.7g\n", mu0[i1]);
printf(" G0(Cl-) = %14.7g\n", mu0[i2]);
i1 = HMW->speciesIndex("H+");
i2 = HMW->speciesIndex("H2O(L)");
j1 = HMW->speciesIndex("OH-");
if (i1 == npos || i2 == npos || j1 == npos) {
printf("problems\n");
exit(-1);
}
deltaG = mu0[j1] + mu0[i1] - mu0[i2];
printf(" OH-: H2O(L) - H+ -> OH-: %14.7g kJ/gmol \n",
deltaG);
printf(" : %14.7g (dimensionless) \n",
deltaG/RT);
printf(" : %14.7g (dimensionless/ln10) \n",
deltaG/(RT * log(10.0)));
printf(" G0(OH-) = %14.7g\n", mu0[j1]);
printf(" G0(H+) = %14.7g\n", mu0[i1]);
printf(" G0(H2O(L)) = %14.7g\n", mu0[i2]);
printf("------------------------------------------------------------\n");
delete HMW;
HMW = 0;
Cantera::appdelete();
return retn;
} catch (CanteraError& err) {
std::cout << err.what() << std::endl;
return -1;
}
}
int main(int argc, char **argv)
{
int retn = 0;
int i;
try {
char iFile[80];
strcpy(iFile, "HMW_NaCl.xml");
if (argc > 1) {
strcpy(iFile, argv[1]);
}
double Cp0_R[20], pmCp[20];
//fileLog *fl = new fileLog("HMW_graph_1.log");
//setLogger(fl);
HMWSoln *HMW = new HMWSoln(iFile, "NaCl_electrolyte");
/*
* Load in and initialize the
*/
Cantera::ThermoPhase *solid = newPhase("NaCl_Solid.xml","NaCl(S)");
int 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;
act[i] = 0.0;
}
HMW->getMoleFractions(mf);
string sName;
TemperatureTable TTable(15, false, 273.15, 25., 0, 0);
HMW->setState_TP(298.15, 1.01325E5);
int i1 = HMW->speciesIndex("Na+");
int i2 = HMW->speciesIndex("Cl-");
//int i3 = HMW->speciesIndex("H2O(L)");
for (i = 0; i < nsp; i++) {
moll[i] = 0.0;
}
HMW->setMolalities(moll);
double ISQRT;
double Is = 0.0;
/*
* Set the Pressure
*/
double pres = OneAtm;
/*
* Fix the molality
*/
Is = 6.146;
ISQRT = sqrt(Is);
moll[i1] = Is;
moll[i2] = Is;
HMW->setState_TPM(298.15, pres, moll);
double Xmol[30];
HMW->getMoleFractions(Xmol);
ThermoPhase *hmwtb = (ThermoPhase *)HMW;
ThermoPhase *hmwtbDupl = hmwtb->duplMyselfAsThermoPhase();
//ThermoPhase *hmwtbDupl = 0;
HMWSoln *HMW1 = HMW;
HMWSoln *HMW2 = dynamic_cast<HMWSoln *>(hmwtbDupl);
for (int itherms = 0; itherms < 2; itherms++) {
if (itherms ==0) {
HMW = HMW1;
} else {
HMW = HMW2;
}
/*
* 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;
if (itherms ==0) {
ttt = fopen("table1.csv","w");
} else {
ttt = fopen("table2.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 (int k = 0; k < nsp; k++) {
Cp0_R[k] *= GasConstant * 1.0E-6;
}
molarCp0 = 0.0;
for (int k = 0; k < nsp; k++) {
molarCp0 += Xmol[k] * Cp0_R[k];
}
if (i != TTable.NPoints+1) {
printf("%13g, %13g, %13g, %13g, %13g, %13g, "
"%13g, %13g, %13g, %13g\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("%13g %13g %13g %13g %13g\n", Xmol[0], moll[0], Cp0_H2O , Cp_H2O, Cp_H2O-Cp0_H2O);
printf(" Na+ ");
printf("%13g %13g %13g %13g %13g\n", Xmol[i1], moll[i1],
Cp0_Naplus , Cp_Naplus, Cp_Naplus -Cp0_Naplus);
printf(" Cl- ");
printf("%13g %13g %13g %13g %13g\n", Xmol[i2], moll[i2],
Cp0_Clminus , Cp_Clminus, Cp_Clminus - Cp0_Clminus);
printf(" NaCl(s)");
printf("%13g %13g %13g %13g\n", 1.0,
Cp0_NaCl , Cp_NaCl, Cp_NaCl - Cp0_NaCl);
#ifdef DEBUG_HKM
fclose(ttt);
#endif
}
delete HMW1;
HMW = 0;
delete hmwtbDupl;
hmwtbDupl = 0;
delete solid;
solid = 0;
Cantera::appdelete();
return retn;
} catch (CanteraError) {
printf("caught error\n");
showErrors();
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;
}
}