A Simultaneous Interpretation of Existing Data on Non-Ideality of Gases and Solutions; Simple Equations of State Without Empirical Concepts and Parameters; Langmuir Isotherm for Three Dimensions (Dedicated to the Memory of J.H. Van’t Hoff)

Authors: Raji Heyrovska

Existing data on the actual pressure, volume, temperature (for gases) and osmotic pressure, molar volume, temperature (for solutions) are described by simple analogous equations of state, valid for low as well as high concentrations. Deviations from ideality are ascribed to a) the volume of gas molecules, b) solvation and c) molecular and ionic association and dissociation as a result of intermolecular and interionic forces.Other main findings supporting the above conclusions are 1) a simple quantitative relation between equivalent conductivity, degree of dissociation and osmotic pressure, 2) linear dependence of the product of concentration and the coefficients of diffusion and viscosity on the osmotic pressure, 3) linear dependence of the e.m.f. of concentration cells on the logarithm of osmotic pressure, with the slope depending on solvent polarization and 4) quantitative fit of the Langmuir isotherm for occupation of space. As a consequence of the above, representation of non-ideality by activity and fugacity coefficients is not necessary. (This was originally submitted to Coll.Czechsl.Chem.Communs. in 1984, see comments.)

Comments: 46 Pages. This fundamental paper in 1984, was approved by the Editor but not by the referee. Eventually published elsewhere: Complete list in:

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[v1] 2017-12-05 09:31:43

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