Application of Kirkwood–Buff theory to free energies of transfer of electrolytes from one solvent to another

Abstract

Solute n.m.r. may be used to obtain quantitative information concerning the preferential solvation of alkali metal and halide ions in binary solvent mixtures. Using the exact theory due to Kirkwood and Buff one can relate the n.m.r. data to the free energies of transfer of individual ions from one pure solvent to another or to the binary mixture. The results obtained are similar although not identical to less rigorous approaches published earlier. The results obtained, when combined to give data for neutral combinations of ions, may be compared with thermodynamically measured free energies of transfer.