278 lines
8.5 KiB
C++
278 lines
8.5 KiB
C++
/**
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* @file HMW_graph_VvT
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*/
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#include "cantera/thermo.h"
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#include "TemperatureTable.h"
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#include "cantera/thermo/HMWSoln.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 V0[20], pmV[20];
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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 acMol[100];
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//double act[100];
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double mf[100];
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double moll[100];
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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 = 0; 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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/*
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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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double 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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double meanMW = HMW->meanMolecularWeight();
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/*
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* ThermoUnknowns
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*/
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double T;
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double V0_NaCl = 0.0, V0_Naplus = 0.0, V0_Clminus = 0.0, Delta_V0s = 0.0, V0_H2O = 0.0;
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double V_NaCl = 0.0, V_Naplus = 0.0, V_Clminus = 0.0, V_H2O = 0.0;
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double molarV0;
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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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printf("A_V : Comparison to Pitzer's book, p. 99, can be made.\n");
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printf(" Agreement to 3 sig digits \n");
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printf("\n");
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printf("Delta_V0: Heat Capacity 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_Vs: Delta volume 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("phiV: phiV, calculated from the program, is checked\n");
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printf(" against analytical formula in V_standalone program.\n");
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printf(" (comparison against Pitzer book, p. 97, eqn. 96)\n");
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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_V,"
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" Delta_V0,"
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" Delta_Vs, Vex, phiV,"
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" MolarV, MolarV0\n");
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printf(" Kelvin, bar, sqrt(kg/gmol),sqrt(kg/gmol)cm3/gmol,"
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"cm**3/gmolSalt,"
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"cm**3/gmolSalt,cm**3/gmolSoln,cm**3/gmolSalt,"
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"cm**3/gmol, cm**3/gmol\n");
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#ifdef DEBUG_HKM
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fprintf(ttt,"T, Pres, A_V, Vex, phiV, MolarV, MolarV0\n");
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fprintf(ttt,"Kelvin, bar, sqrt(kg/gmol)cm3/gmol, cm3/gmolSoln, cm3/gmolSalt, kJ/gmolSoln,"
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"kJ/gmolSoln\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 volumes m3/kmol
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*/
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solid->getStandardVolumes(V0);
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V0_NaCl = V0[0];
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HMW->getStandardVolumes(V0);
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V0_H2O = V0[0];
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V0_Naplus = V0[i1];
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V0_Clminus = V0[i2];
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/*
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* Calculate the standard state volume change of solution
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* for NaCl(s) -> Na+ + Cl-
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* units: m3 / kmol
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*/
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Delta_V0s = V0_Naplus + V0_Clminus - V0_NaCl;
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double dd = solid->density();
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double MW_NaCl = solid->meanMolecularWeight();
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V_NaCl = MW_NaCl / dd;
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//printf("V_NaCl = %g , V0_NaCl = %g %g\n", V_NaCl, V0_NaCl, 1.0/solid->molarDensity());
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/*
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* Get the partial molar volumes
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*/
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HMW->getPartialMolarVolumes(pmV);
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V_H2O = pmV[0];
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V_Naplus = pmV[i1];
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V_Clminus = pmV[i2];
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//double Delta_V_Salt = V_NaCl - (V_Naplus + V_Clminus);
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/*
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* Calculate the molar volume of solution
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*/
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double dsoln = HMW->density();
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meanMW = HMW->meanMolecularWeight();
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double molarV = meanMW / dsoln;
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//double md = HMW->molarDensity();
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//printf("compare %g %g\n", molarV, 1.0/md);
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/*
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* Calculate the delta volume of solution for the reaction
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* NaCl(s) -> Na+ + Cl-
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*/
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double Delta_Vs = (Xmol[0] * V_H2O +
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Xmol[i1] * V_Naplus +
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Xmol[i2] * V_Clminus
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- Xmol[0] * V0_H2O
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- Xmol[i1] * V_NaCl);
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Delta_Vs /= Xmol[i1];
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/*
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* Calculate the apparent molar volume, J, from the
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* partial molar quantities, units m3/kmol
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*/
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double Vex = (Xmol[0] * (V_H2O - V0_H2O) +
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Xmol[i1] * (V_Naplus - V0_Naplus) +
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Xmol[i2] * (V_Clminus - V0_Clminus));
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/*
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* Calculate the apparent relative molal volume, phiV,
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* units of m3/kmol
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*/
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double phiV = Vex / Xmol[i1];
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double Aphi = HMW->A_Debye_TP(T, pres) / 3.0;
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//double AL = HMW->ADebye_L(T,pres);
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double Av = HMW->ADebye_V(T, pres) * 1.0E3;
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molarV0 = 0.0;
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for (size_t k = 0; k < nsp; k++) {
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molarV0 += Xmol[k] * V0[k];
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}
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if (i != TTable.NPoints+1) {
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printf("%13g, %13g, %13g, %13g, %13g, %13g, "
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"%13.5g, %13g, %13g, %13g\n",
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T, pres*1.0E-5, Aphi, Av, Delta_V0s*1.0E3, Delta_Vs*1.0E3,
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Vex*1.0E3, phiV*1.0E3, molarV*1.0E3 , molarV0*1.0E3);
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#ifdef DEBUG_HKM
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fprintf(ttt,"%g, %g, %g, %g, %g, %g, %g\n",
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T, pres*1.0E-5, Av, Vex*1.0E3, phiV*1.0E3, molarV*1.0E3 , molarV0*1.0E3);
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#endif
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}
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}
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printf("Breakdown of Volume Calculation at 323.15 K, 1atm:\n");
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printf(" Species MoleFrac Molal V0 "
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" partV (partV - V0)\n");
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printf(" H2O(L)");
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printf("%13g %13g %13g %13g %13g\n", Xmol[0], moll[0], V0_H2O*1.E3, V_H2O*1.E3,
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(V_H2O-V0_H2O)*1.E3);
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printf(" Na+ ");
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printf("%13g %13g %13g %13g %13g\n", Xmol[i1], moll[i1],
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V0_Naplus*1.E3 , V_Naplus*1.E3, (V_Naplus -V0_Naplus)*1.E3);
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printf(" Cl- ");
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printf("%13g %13g %13g %13g %13g\n", Xmol[i2], moll[i2],
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V0_Clminus*1.E3, V_Clminus*1.E3, (V_Clminus - V0_Clminus)*1.E3);
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printf(" NaCl(s)");
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double dd = V_NaCl*1.E3 - V0_NaCl*1.E3;
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if (fabs(dd) < 1.0E-12) {
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dd = 0.0;
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}
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printf("%13g %13g %13g %13g\n", 1.0,
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V0_NaCl*1.E3 , V_NaCl*1.E3, dd);
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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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