263 lines
8 KiB
C++
263 lines
8 KiB
C++
/**
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* @file HMW_graph_1.cpp
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*/
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#include "cantera/thermo.h"
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#include "cantera/thermo/HMWSoln.h"
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#include "TemperatureTable.h"
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#include <cstdio>
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using namespace std;
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using namespace Cantera;
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int main(int argc, char** argv)
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{
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int retn = 0;
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size_t i;
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try {
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char iFile[80];
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strcpy(iFile, "HMW_NaCl.xml");
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if (argc > 1) {
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strcpy(iFile, argv[1]);
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}
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double Enth0_RT[20], pmEnth[20], molarEnth;
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HMWSoln* HMW = new HMWSoln(iFile, "NaCl_electrolyte");
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/*
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* Load in and initialize the
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*/
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Cantera::ThermoPhase* solid = newPhase("NaCl_Solid.xml","NaCl(S)");
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size_t nsp = HMW->nSpecies();
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double mf[100];
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double moll[100];
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for (i = 0; i < 100; i++) {
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mf[i] = 0.0;
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moll[i] = 0.0;
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}
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HMW->getMoleFractions(mf);
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string sName;
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TemperatureTable TTable(15, false, 273.15, 25., 0, 0);
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HMW->setState_TP(298.15, 1.01325E5);
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size_t i1 = HMW->speciesIndex("Na+");
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size_t i2 = HMW->speciesIndex("Cl-");
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//int i3 = HMW->speciesIndex("H2O(L)");
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for (i = 1; i < nsp; i++) {
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moll[i] = 0.0;
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}
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HMW->setMolalities(moll);
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double Is = 0.0;
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/*
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* Set the Pressure
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*/
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double pres = OneAtm;
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/*
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* Fix the molality
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*/
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Is = 6.146;
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moll[i1] = Is;
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moll[i2] = Is;
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HMW->setState_TPM(298.15, pres, moll);
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double Xmol[30];
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HMW->getMoleFractions(Xmol);
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/*
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* ThermoUnknowns
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*/
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double T;
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double H0_NaCl = 0.0, H0_Naplus = 0.0, H0_Clminus = 0.0, Delta_H0s, H0_H2O = 0.0;
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double H_NaCl = 0.0, H_Naplus = 0.0, H_Clminus = 0.0, H_H2O = 0.0;
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double molarEnth0;
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printf("A_L/RT: Comparison to Pitzer's book, p. 99, can be made.\n");
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printf(" Agreement to 3-4 sig digits for Aphi and A_L/RT\n");
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printf("\n");
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printf("Delta_H0: Heat of Solution per mole of salt (standard states)\n");
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printf(" rxn for the ss heat of soln: "
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"NaCl(s) -> Na+(aq) + Cl-(aq)\n");
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printf("\n");
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printf("Delta_Hs: Heat of Solution per mole of salt\n");
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printf(" rxn for heat of soln: "
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" n1 H2O(l,pure) + n2 NaCl(s) -> n2 MX(aq) + n1 H2O(l) \n");
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printf(" Delta_Hs = (n1 h_H2O_bar + n2 h_MX_bar "
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"- n1 h_H2O_0 - n2 h_MX_0)/n2\n");
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printf("\n");
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printf("phiL: phiL, calculated from the program, is checked\n");
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printf(" against analytical formula in L_standalone program.\n");
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printf(" (comparison against Eq. 12, Silvester and Pitzer)\n");
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#ifdef DEBUG_HKM
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FILE* ttt = fopen("table.csv","w");
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#endif
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/*
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* Create a Table of NaCl Enthalpy Properties as a Function
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* of the Temperature
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*/
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printf("\n\n");
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printf(" T, Pres, Aphi, A_L/RT,"
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" Delta_H0,"
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" Delta_Hs, L, phiL,"
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" L_rel_molal,"
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" MolarEnth, MolarEnth0\n");
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printf(" Kelvin, bar, sqrt(kg/gmol), sqrt(kg/gmol),"
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" kJ/gmolSalt,"
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" kJ/gmolSalt, kJ/gmolSoln, kJ/gmolSalt,"
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" kJ/gmolSalt, kJ/gmol, kJ/gmol\n");
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#ifdef DEBUG_HKM
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fprintf(ttt,"T, Pres, A_L/RT, Delta_H0, Delta_Hs, phiL\n");
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fprintf(ttt,"Kelvin, bar, sqrt(kg/gmol), kJ/gmolSalt, kJ/gmolSalt, kJ/gmolSalt\n");
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#endif
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for (i = 0; i < TTable.NPoints + 1; i++) {
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if (i == TTable.NPoints) {
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T = 323.15;
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} else {
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T = TTable.T[i];
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}
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/*
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* RT is in units of J/kmolK
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*/
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double RT = GasConstant * T;
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/*
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* Make sure we are at the saturation pressure or above.
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*/
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double psat = HMW->satPressure(T);
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pres = OneAtm;
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if (psat > pres) {
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pres = psat;
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}
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HMW->setState_TPM(T, pres, moll);
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solid->setState_TP(T, pres);
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/*
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* Get the Standard State DeltaH
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*/
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solid->getEnthalpy_RT(Enth0_RT);
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H0_NaCl = Enth0_RT[0] * RT * 1.0E-6;
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HMW->getEnthalpy_RT(Enth0_RT);
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H0_H2O = Enth0_RT[0] * RT * 1.0E-6;
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H0_Naplus = Enth0_RT[i1] * RT * 1.0E-6;
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H0_Clminus = Enth0_RT[i2] * RT * 1.0E-6;
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/*
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* Calculate the standard state heat of solution
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* for NaCl(s) -> Na+ + Cl-
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* units: kJ/gmolSalt
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*/
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Delta_H0s = H0_Naplus + H0_Clminus - H0_NaCl;
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solid->getPartialMolarEnthalpies(pmEnth);
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H_NaCl = pmEnth[0] * 1.0E-6;
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HMW->getPartialMolarEnthalpies(pmEnth);
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H_H2O = pmEnth[0] * 1.0E-6;
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H_Naplus = pmEnth[i1] * 1.0E-6;
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H_Clminus = pmEnth[i2] * 1.0E-6;
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//double Delta_H_Salt = H_NaCl - (H_Naplus + H_Clminus);
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//double Lfunc = HMW->relative_enthalpy() * 1.0E-6;
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molarEnth = HMW->enthalpy_mole() * 1.0E-6;
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double Delta_Hs = (Xmol[0] * H_H2O +
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Xmol[i1] * H_Naplus +
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Xmol[i2] * H_Clminus
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- Xmol[0] * H0_H2O
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- Xmol[i1] * H_NaCl);
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Delta_Hs /= Xmol[i1];
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/*
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* Calculate the relative enthalpy, L, from the
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* partial molar quantities. units kJ/gmolSolution
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*/
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double L = (Xmol[0] * (H_H2O - H0_H2O) +
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Xmol[i1] * (H_Naplus - H0_Naplus) +
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Xmol[i2] * (H_Clminus - H0_Clminus));
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/*
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* Calculate the apparent relative molal enthalpy, phiL,
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* units of kJ/gmolSaltAdded
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*/
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double phiL = L / Xmol[i1];
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double Aphi = HMW->A_Debye_TP() / 3.0;
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double AL = HMW->ADebye_L();
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double LrelMol = HMW->relative_molal_enthalpy() * 1.0E-6;
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for (size_t k = 0; k < nsp; k++) {
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Enth0_RT[k] *= RT * 1.0E-6;
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}
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molarEnth0 = 0.0;
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for (size_t k = 0; k < nsp; k++) {
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molarEnth0 += Xmol[k] * Enth0_RT[k];
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}
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if (i != TTable.NPoints+1) {
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printf("%13.4f, %13.4f, %13.4f, %13.4f, %13.4f, %13.4f, %13.4f, "
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"%13.4f, %13.4f, %13.4f, %13.4f\n",
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T, pres*1.0E-5, Aphi, AL/RT, Delta_H0s, Delta_Hs,
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L, phiL,
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LrelMol,
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molarEnth , molarEnth0);
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#ifdef DEBUG_HKM
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fprintf(ttt,"%g, %g, %g, %g, %g, %g\n",
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T, pres*1.0E-5, AL/RT, Delta_H0s, Delta_Hs, phiL);
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#endif
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}
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}
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printf("Breakdown of Enthalpy Calculation at 323.15 K, 1atm:\n");
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printf(" Species MoleFrac Molal H0 "
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" partH (partH - H0)\n");
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printf(" H2O(L)");
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printf("%13.4f %13.4f %13.4f %13.4f %13.4f\n", Xmol[0], moll[0], H0_H2O , H_H2O, H_H2O-H0_H2O);
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printf(" Na+ ");
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printf("%13.4f %13.4f %13.4f %13.4f %13.4f\n", Xmol[i1], moll[i1],
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H0_Naplus , H_Naplus, H_Naplus -H0_Naplus);
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printf(" Cl- ");
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printf("%13.4f %13.4f %13.4f %13.4f %13.4f\n", Xmol[i2], moll[i2],
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H0_Clminus , H_Clminus, H_Clminus - H0_Clminus);
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delete HMW;
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HMW = 0;
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delete solid;
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solid = 0;
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Cantera::appdelete();
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#ifdef DEBUG_HKM
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fclose(ttt);
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#endif
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return retn;
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} catch (CanteraError& err) {
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std::cout << err.what() << std::endl;
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Cantera::appdelete();
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return -1;
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}
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}
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