This is the classic problem of the solubility of NaCl in water. The result is a saturated solution of Na+ and Cl- in water in equilibrium with NaCl solid. This problem also has a gas phase consisting of N2, H2O, H2, and O2. CO2 has been thrown in as well. However, the element abundance of C is zero. So, CO2 should turn out to have a zero concentration. The problem can be divided up into two parts: estimating the Gibbs reaction delta for Na+ + Cl- = NaCl(solid) (so that Del(Gf) = G(NaCl(solid)) - G(Na+) - G(Cl-)) and estimating the activity coefficients for the electrolytes at the solubility limit. By far the most important as always is estimating the delta G for the reaction above. Note the electrolytes are using the molality basis. Using the NASA basis we get NaCl(solid) : Hf(298.15) = -411.1207 kJ/gmol S(298.15) = 72.1093 J/(gmol K) (from NIST Webbook) Gf(298.15) = -432.6200 kJ/gmol From Codata key values for Thermodynamics: Cl- Hf(298.15) = -167.080 kJ/gmol S(298.15) = 56.60 J/(gmol K) Gf(298.15) = -183.9552 kJ/gmol Na+ Hf(298.15) = -240.34 kJ/gmol S(298.15) = 58.45 J/(gmol K) -> Gf(298.15) = -257.7668 kJ/gmol Del(Gf)(298.15) = 9.1020 kJ/gmol In addition, the relative humidity of the salt solution may be compared to the humidity above a pure water solution in order to understand the effects of the lowering of the water activity. If you run the equilibrium calculation without salt, you get the equilibrium of water vapor above water, consistent with the current thermo. X_H2O(g) = 0.03169 at 25C and 1atm If you then run the calculation with a saturated salt solution you get a smaller amount of water vapor in equilibrium with the water electrolyte: X_H2O(g) = 0.023243 at 25V and 1atm The ratio of these two numbers is the relative humidity at which the a saturated salt solution deliqueses from a salt particle. rel humidity = 0.733 This is a very important number in terms of its effect on aqueous corrosion. Next, let's compare the above calculation with the calculation presented in the current directory. First, getting Gabs from the cttables calculation: G(298.15) NaCl(solid) = -432.6201 kJ/gmol G(298.15) Na+ = -257.7668 kJ/gmol G(298.15) Cl- = -183.9552 kJ/gmol (note, Na+ and Cl- have screwed up H and S values. However, the G value seems to be correct). Putting this together yields: Delta G = 9.1019 kJ / gmol ---------------------------------------------------------------------------- H2O(l) = H+ + OH- Equilibrium Reaction ------------------------------------------------------------------------ The equilibrium constant for water is given in Robinson and Stokes, p. 363 and p.544. 10^(-13.996) = actCoef(H+) actCoef(OH-) Molal(H+) Molal(OH-) / activity_H2O. This works out to a value of DeltaG = 79.88936 kJ/gmol DeltaH = 56.576 kJ/gmol DeptaCp = -194.68 J/K gmol In the current database: G(298, OH-) = -226.7839 kJ / gmol G(298 H+) = 0.0 G(298, H2O(L)) = -306.6858. ------------------------- DeltaG = 79.902 Therefore, there is a slight error of 0.013 kJ/gmol, but the database is roughly correct. Silvestre & Pitzer ------------------------------------------------------------------------ The equilibrium condition for this simple system comes down to the following equation Delta G = - 2 R T ln (m * actCoeff) This is the basic test of the system. Delta G = -2161 cal gmol-1 = -9.0416 kJ gmol-l M_sat = 6.146 ActCoeff_mixed_molalityScale = 1.008 Using the given files and conditions, I calculate equilibrium as: Delta G = 9.1019 kJ gmol-l M_sat = 6.193 ActCoeff_mixed_molalityScale = 1.0132 Relative Humidity Lowering ------------------------------------------------------ from the saturated NaCl calculation using HMW x_H2O = 0.0237641 From the pure water equilibrium case: x_H2O = 0.0316882 Therefore the relative humidity lowering is 0.7504