Study of experimental-to-McMillan–Mayer conversion of thermodynamic excess functions

The problem of the conversion of excess thermodynamic functions, namely the osmotic coefficient and the mean activity coefficient, from the so-called Lewis–Randall (experimental) system to the McMillan–Mayer system has been reconsidered. This correction should be used whenever departures from ideality in ionic solutions are interpreted at the McMillan–Mayer level, in the framework of the primitive model in which the solvent is regarded as a continuum. New general equations and simple approximate expressions have been derived. The latter formulae yield fairly accurate results for the variety of salts considered. Moreover, an important property of these relationships is that they satisfy the Gibbs–Duhem equation. It is found that the corrections caused by the conversion can be significant for concentrations typically above 0.5–1 mol kg–1.

[1]  P. Turq,et al.  REAL IONIC SOLUTIONS IN THE MEAN SPHERICAL APPROXIMATION. 1. SIMPLE SALTS IN THE PRIMITIVE MODEL , 1996 .

[2]  J. Simonin,et al.  Departures from ideality in pure ionic solutions using the mean spherical approximation , 1996 .

[3]  J. Barthel,et al.  Lithium bromide in acetonitrile: Thermodynamics, theory, and simulation , 1991 .

[4]  R. Goldberg.  Evaluated activity and osmotic coefficients for aqueous solutions: bi‐univalent compounds of lead, copper, manganese, and uranium , 1979 .

[5]  M. Floriano,et al.  Simple electrolytes in the mean spherical approximation. 2. Study of a refined model , 1978 .

[6]  M. Floriano,et al.  Simple electrolytes in the mean spherical approximation. III. A workable model for aqueous solutions , 1977 .

[7]  J. R. Grigera,et al.  Simple electrolytes in the mean spherical approximation , 1976 .

[8]  G. Stell.  Ionic solution theory for nonideal solvents , 1973 .

[9]  Harold L. Friedman,et al.  Lewis-Randall to McMillan-Mayer conversion for the thermodynamic excess functions of solutions. Part I. Partial free energy coefficients , 1972 .

[10]  J. Rasaiah.  Computations for Higher Valence Electrolytes in the Restricted Primitive Model , 1972 .

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

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

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

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

[15]  R. E. Gibson.  Influence of the concentration and nature of the solute on the compressions of certain aqueous salts. [1 to 1000 bars, 25/sup 0/C, experimental and calculated data] , 1935 .

[16]  R. E. Gibson.  The Influence of Concentration on the Compressions of Aqueous Solutions of Certain Sulfates and a Note on the Representation of the Compressions of Aqueous Solutions as a Function of Pressure1 , 1934 .