Thermodynamic functions of transfer of single ions from water to nonaqueous and mixed solvents: Part I - Gibbs free energies of transfer to nonaqueous solvents

Abstract

Abstract

An Electrochemical Understanding of Extraction of Silver Picrate by Benzo-3<i>m</i>-Crown-<i>m</i> Ethers (<i>m</i> = 5, 6) into 1,2-Dichloroethane and Dichloromethane

“…Using Equation (13), the ∆φ eq values corresponding to the differences with S D,Pic log K were evaluated. Here, the 0 Pic φ ′ ∆ values employed for the ∆φ eq evaluation were −0.0598 V [6] for the w/DCE system and −0.040 2 [11] for the w/DCM one; these standard formal or ion transfer potentials [8] have been directly or indirectly determined based on the extra-thermodynamic assumption for 4 4 Ph As BPh [5]- [7]. c Values standardized with Equation (9) Table 2 for the other values.…”

The transfer of neutral molecules, ions and ionic species from water to benzonitrile; comparison with nitrobenzene

“…3 for the partition of ions and ionic species. Marcus [32,33] records Gibbs energies of transfer of a few ions from water to benzonitrile, but these are either calculated in some way, or are observed values, but not on the TATB convention. However, Gibbs energies of transfer on the TATB convention were subsequently determined by Namor and Ponce [34,35] from measurements of solubilities of 1:1 electrolytes.…”

“…It would be especially interesting to be able to compare the ionic coefficients j + and j -for partition to benzonitrile with those for partition to nitrobenzene. Marcus [33] listed data for transfer of a few ions to nitrobenzene, but later on Namor et al [38] used the solubility method to obtain data for a range of ions. Herrera et al [39], rather oddly, repeated the work of Namor et al [38] but added nothing of significance and so we just use the data of Namor et al [38] for transfer to dry nitrobenzene.…”

Thermodynamic functions of transfer of single ions from water to nonaqueous and mixed solvents: Part 4 - The selection of extra thermodynamic assumptions

“…16 neu A major difficulty with this treatment arises from the fact that dielectric saturation sets in near the ion for ions as small as the crystal ionic radius implies. Thus the bulk relative permittivity is not the appropriate quantity to be used in the electrostatic expression (6). Either the radii r. and r.…”

“…Conway1 has summarized the merits of, and difficulties with, these assumptions with regard to the hydration of ions (i.e., their solvation by water), and has made some recommendations. Parker and Alexander2 have examined some of the proposed methods regarding (ion, S1 --S2), and more comprehensive comparisons and evaluations have been made by Popovych3' and Marcusb, among others. In recent publications the present author presented a compilation of data on tG (ions, W÷S) 6 and H (ions, W -S), where W denotes water and S a nonaqueous solvent. He also evaluated these ata on the basis of preferred extrathermodynamic assumptions, and arrived at a set of selected data that he recommended.…”