David N. Glew

Evaluation of the Thermodynamic Functions for Aqueous Sodium Chloride from Equilibrium and Calorimetric Measurements below 154 °C

A new weighted least‐squares method is described which is generally applicable for the nonsubjective evaluation of the best set of thermodynamic functions from a given data set of equilibrium (ΔG) and calorimetric (ΔH, Cp) measurements. The method, applied to model a wide range of 2428 measurements for the water‐sodium chloride system between −21 and 154 °C, accurately represents all measurements within experimental error. The resulting model is used to predict the thermodynamic functions and their standard errors for aqueous sodium chloride up to 110 °C. Tables are given for freezing point, solubility, boiling point, osmotic and activity coefficients, vapor pressure, apparent molal relative enthalpy, partial molal relative enthalpies, integral heat of solution, specific heat, apparent molal heat capacity, partial molal heat capacities, apparent molal relative heat capacity, partial molal relative heat capacities, standard thermodynamic functions, and their changes for dissolution.

Evaluation of Debye–Hückel limiting slopes for water between 0 and 150°C

Debye–Huckel limiting slopes for the osmotic coefficient, A, derived from literature measurements of the static dielectric constant and density of water, are properly represented as a function of temperature by a general thermodynamic equation, determined using the method of weighted least-squares. From 0 to 150°C and between atmospheric and the water-saturation pressure, A is best represented by an equation equivalent to A=–16.390 23 + 261.3371/T+ 3.368 9633 ln T–1.437 167(T/100)+ 0.111 995(T/100)2 where T/K = 273.15 +t/°C IPTS-68. Minimum variance, unbiased estimates of the values and their standard errors are tabulated for A and for the limiting slopes for the solute enthalpy, AL, and heat capacity, AJ.