Solvation Phenomena of Potassium Thiocyanate in Methanol–Water Mixtures

This paper reports the results of a variety of experiments carried out for understanding the solvation behavior of potassium thiocyanate in methanol–water mixtures. Electrical conductivity, speed of sound, viscosity, and FT-Raman spectra of potassium thiocyanate solutions in 5 and 10% methanol–water (w/w) mixtures were measured as functions of concentration and temperature. The conductivity and structural relaxation time suggest the ion–solvent and solvent-separated ion–ion associations increase as the salt concentration increases in the mixtures. The Raman band shifts due to the C----O stretching mode of methanol for the solvent mixtures reveal the formation of methanol–water complexes. The significant changes in the Raman bands for the C----N, C----S and O----H stretching modes indicate the presence of SCN−−solvent interactions through the Nend, “free” SCN− and the solvent-shared ion pairs as potassium thiocyanate is added to the methanol–water mixtures. The relative changes corresponding to H----O----H bending and C----O stretching frequencies indicate that K+ is preferentially solvated by water in these solvent mixtures. The appearance and increase of the intensity of a broad band at ≈940 cm−1 upon salt addition was attributed to the SCN−–H2O----K+ solvent-shared ion pairs. No Raman spectral evidence for K+(H2O)n species was observed. The preferential solvation of K+ and SCN− in the methanol−water mixtures was verified by the application of the Kirkwood−Buff theory of solutions. This theory confirms that K+ is strongly preferentially solvated by water, whereas SCN− is preferentially solvated by the methanol component.