By Mellor J.W
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Additional info for A Comprehensive Treatise On Inorganic And Theoretical Chemistry
13 Here, ion paring with the characteristic entropy-driving force occurs only at higher pH; at lower pH, hydrogen bonding with the electroneutral free acid takes over. 2) which both describe the dependence of K on the dielectricity constant ε and the permanent ion charges zA and zB; the parameters Q and a characterize the distance between the ions. Indeed, one ﬁnds with a multitude of experimental data a fairly linear dependence between log K and zAzB (Fig. 5). 2 already suggest that in a most simple description each ion pair contributes—within the same geometrically matching complex— the same binding increment.
1 V deemed to be the most nearly correct one. So-called “real” standard molar Gibbs energies of hydration are obtained from the electromotive force of cells consisting of a downward ﬂowing jet of aqueous solution and a solution along the surface of a tube concentric with the jet, with a small air (vapor) gap between them. 3 C mol−1 is Faraday’s constant. The uncertainties connected with the value of Δχ make the use of the measurable “real” standard molar Gibbs energies of hydration unattractive for obtaining individual ionic values for the desired quantity, Δ hydrGI∞.
A brief account of the relevant ion properties in such environments is presented here. 3 concerning hydration numbers. More deﬁnite are the thermodynamic quantities related to the transfer of ions from a source solvent, say water, to a target solvent or solvent mixture. As for the thermodynamic quantities characterizing ions in aqueous solutions dealt with above, also the transfer quantities can be measured for entire electrolytes only, and an extrathermodynamic assumption is required in order to describe the transfer properties of individual ions.