Study of a Refined Model for Aqueous 1‐1 Electrolytes

The hypernetted‐chain integral equation is used to calculate the ion–ion pair correlation functions and the thermodynamic properties of models for aqueous alkali halides based on an ion–ion pair potential function having four terms: the usual Coulomb term, a core repulsion term of order r−9, a well‐known dielectric repulsion term of order r−4, and a “Gurney” term to represent the effect of the overlap of the structure‐modified regions, “cospheres,” about the ions when the ions come close together. The only parameter in the potential which is adjusted to fit excess free energy data for solutions is the coefficient Aij of the Gurney term for the interaction of ions of species i and j. This is scaled so it represents the molar free energy change of water displaced from the cospheres when they overlap. The corresponding entropy change Sij and volume change Vij are adjusted to fit, respectively, heat of dilution and apparent molal volume data. Some thermodynamic problems in this fitting process, due to the und...

[1]  J. Rasaiah.  Equilibrium Properties of Ionic Solutions; The Primitive Model and its Modification for Aqueous Solutions of the Alkali Halides at 25°C , 1970 .

[2]  R. Gurney.  Ionic processes in solution , 1953 .

[3]  B. S. Snowden,et al.  Nuclear Spin–Lattice Relaxation in LiCl Solutions , 1968 .

[4]  H. Hertz,et al.  Elementarvorgänge in der Hydrathülle von Ionen aus Protonen- und Deuteronenrelaxationszeiten , 1963 .

[5]  W. M. Latimer,et al.  Heats and Entropies of Successive Steps in the Formation of AIF6 , 1953 .

[6]  D. N. Card,et al.  Monte Carlo Study of the Thermodynamics of Electrolyte Solutions , 1970 .

[7]  H. Friedman,et al.  Cluster Expansion Methods for Systems of Polar Molecules: Some Solvents and Dielectric Properties , 1963 .

[8]  R. Marcus.  Interactions in Polar Media. II. Continua , 1963 .

[9]  C. J. Pings,et al.  Analysis of Scattering Data for Mixtures of Amorphous Solids or Liquids , 1968 .

[10]  A. Allnatt.  Integral equations in ionic solution theory , 1964 .

[11]  B. B. Owen,et al.  The Physical Chemistry of Electrolytic Solutions , 1963 .

[12]  H. Friedman,et al.  Nuclear Magnetic Relaxation in Ionic Solution. I. Relaxation of 23Na in Aqueous Solutions of NaCl and NaClO4 , 1966 .

[13]  J. C. Poirier.  Thermodynamic Functions from Mayer's Theory of Ionic Solutions. I. Equations for Thermodynamic Functions , 1953 .

[14]  H. Friedman.  Thermodynamic Excess Functions for Electrolyte Solutions , 1960 .

[15]  Brian E. Conway,et al.  Modern Aspects of Electrochemistry , 1974 .

[16]  H. Friedman.  Mayer's Ionic Solution Theory Applied to Electrolyte Mixtures , 1960 .

[17]  H. Friedman,et al.  Integral Equation Methods in the Computation of Equilibrium Properties of Ionic Solutions , 1968 .

[18]  Milton Blander,et al.  Chemical physics of ionic solutions: edited by B. E. Conway and R. G. Barradas. 622 pages, diagrams, illustr. 6 × 9 in. New York, Wiley and Sons, 1966. $25.00 , 1967 .

[19]  H. Friedman,et al.  Integral Equation Computations for Aqueous 1–1 Electrolytes. Accuracy of the Method , 1969 .

[20]  L. Pauling.  The Nature Of The Chemical Bond , 1939 .

[21]  E. A. Guggenheim,et al.  Repulsive energy in sodium chloride and potassium chloride crystals , 1965 .

[22]  D. Ritson,et al.  Dielectric Properties of Aqueous Ionic Solutions. Parts I and II , 1948 .

[23]  W. G. McMillan,et al.  The Statistical Thermodynamics of Multicomponent Systems , 1945 .

[24]  H. Friedman,et al.  Theory of mixed electrolyte solutions and application to a model for aqueous lithium chloride-cesium chloride , 1970 .

[25]  H. Friedman,et al.  Charged square-well model for ionic solutions , 1968 .

[26]  D. F. Evans,et al.  The Conductance of the Tetraalkylammonium Halides in Deuterium Oxide Solutions at 25 , 1965 .

[27]  Henry S. Frank,et al.  Free Volume and Entropy in Condensed Systems III. Entropy in Binary Liquid Mixtures; Partial Molal Entropy in Dilute Solutions; Structure and Thermodynamics in Aqueous Electrolytes , 1945 .

[28]  J. S. Rowlinson,et al.  An equation of state of gases at high temperatures and densities , 1964 .

[29]  R. Zwanzig.  Dielectric Friction on a Moving Ion , 1963 .