257 lines
8.2 KiB
C++
257 lines
8.2 KiB
C++
/**
|
|
*
|
|
* @file HMW_graph_1.cpp
|
|
*/
|
|
|
|
#include "cantera/thermo.h"
|
|
#include "TemperatureTable.h"
|
|
#include "cantera/thermo/HMWSoln.h"
|
|
|
|
#include <cstdio>
|
|
|
|
using namespace std;
|
|
using namespace Cantera;
|
|
|
|
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
|
|
*/
|
|
ThermoPhase* solid = newPhase("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-");
|
|
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);
|
|
|
|
ThermoPhase* hmwtb = (ThermoPhase*)HMW;
|
|
|
|
ThermoPhase* hmwtbDupl = hmwtb->duplMyselfAsThermoPhase();
|
|
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;
|
|
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");
|
|
for (i = 0; i < TTable.NPoints + 1; i++) {
|
|
if (i == TTable.NPoints) {
|
|
T = 323.15;
|
|
} else {
|
|
T = TTable.T[i];
|
|
}
|
|
/*
|
|
* Make sure we are at the saturation pressure or above.
|
|
*/
|
|
pres = std::max(HMW->satPressure(T), OneAtm);
|
|
|
|
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 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("%13.5f, %13.5f, %13.5f, %13.5f, %13.5f, %13.5f, "
|
|
"%13.5f, %13.5f, %13.5f, %13.5f\n",
|
|
T, pres*1.0E-5, Aphi, AJ/GasConstant, Delta_Cp0s, Delta_Cps,
|
|
J, phiJ, molarCp , molarCp0);
|
|
}
|
|
|
|
}
|
|
|
|
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("%13.5f %13.5f %13.5f %13.5f %13.5f\n", Xmol[0], moll[0], Cp0_H2O , Cp_H2O, Cp_H2O-Cp0_H2O);
|
|
printf(" Na+ ");
|
|
printf("%13.5f %13.5f %13.5f %13.5f %13.5f\n", Xmol[i1], moll[i1],
|
|
Cp0_Naplus , Cp_Naplus, Cp_Naplus -Cp0_Naplus);
|
|
printf(" Cl- ");
|
|
printf("%13.5f %13.5f %13.5f %13.5f %13.5f\n", Xmol[i2], moll[i2],
|
|
Cp0_Clminus , Cp_Clminus, Cp_Clminus - Cp0_Clminus);
|
|
|
|
printf(" NaCl(s)");
|
|
printf("%13.5f %13.5f %13.5f %13.5f\n", 1.0,
|
|
Cp0_NaCl , Cp_NaCl, Cp_NaCl - Cp0_NaCl);
|
|
|
|
}
|
|
|
|
delete HMW1;
|
|
HMW = 0;
|
|
delete hmwtbDupl;
|
|
hmwtbDupl = 0;
|
|
delete solid;
|
|
solid = 0;
|
|
appdelete();
|
|
|
|
|
|
return retn;
|
|
|
|
} catch (CanteraError& err) {
|
|
std::cout << err.what() << std::endl;
|
|
appdelete();
|
|
return -1;
|
|
}
|
|
}
|