
%0 Journal Article
%A Wells, CF 
%T The spectrophotometric solvent sorting method for the determination of free energies of transfer of individual ions&#8212;a critical appraisal
%J Australian Journal of Chemistry
%D 1983/09/01
%V 36
%N 9
%P 1739-1752
%K 
%R https://doi.org/10.1071/CH9831739
%U https://www.publish.csiro.au/paper/CH9831739 
%X The spectrophotometric method for determining values for the free energy of transfer of the proton from water into water + co-solvent mixtures at mole fractions of co-solvent up to x2 &#8776; 0.3 is examined critically from first principles. It is found that some corrections become significant at the higher x2 in this range and these are applied to all the co-solvents used. The new values for &#916;Gtº(H+) are then used to calculate new values for &#916;Gtº (X-) from &#916;Gtº(HX) and new values for &#916;Gtº(M+) and (M2+)from &#916;Gtº(MX) and &#916;GTº(MX2). New electrochemical, solubility and pK data are incorporated into these calculations, resulting in &#916;Gtº values for some additional ions for several co-solvents. The &#916;Gtº values for all co-solvents are compared and contrasted, and it is concluded that structural changes in the solvent have a dominant effect in determining these values. The evidence for molecular rearrangements involving solvent molecules in the neighbourhood of the ions resulting from the transfer is examined. 
