Solvation consequences of potassium thiocyanate (KSCN) and tetrabutylammonium thiocyanate
(Bu4NSCN) in γ-butyrolactone (GBL), N,N-dimethylacetamide (DMA) and their binary mixtures in
concentration range (0.01-0.001) mol Kg–1 of 0, 25, 50, 60, 80 and 100 mol% DMA at T = 298.15 K
and 308.15 K have been studied using conductometric study and some samples of KSCN in GBL +
DMA binary mixtures of different electrolytic concentrations at ambient conditions studied by FTIR
spectroscopic methods. The Shedlovsky equation has been used to elucidate the data in terms of the
limiting molar conductances (Λo), ion-pair association constants (KA). The Walden products (Λoηo),
solvated radii (ri) and standard free energies of association (ΔGºA) were further evaluated in terms of
solvation of ions. The reference electrolyte tetrabutylammonium tetraphenylborate (Bu4NBPh4) was
used to determine the limiting molar ionic conductances. In pure solvents and their binary mixtures,
electrolytes showed a strong association. The K+ ions have greater solvation in GBL than in DMA
observed on basis of solvated radii in GBL + DMA binary solvent mixtures at both experimental
temperatures. The study demonstrates that the ion-solvent interactions decrease on enhancing the
temperature. The FTIR analysis was applied to obtain information about molecular as well as ionic
association of KSCN in GBL + DMA binary mixtures at the ambient conditions, which has provided
the information on structuring infrared modes of vibrational stretching frequencies according to the
nature of the solvents or the cations. Shifting of vibrational frequencies of several functional groups of
DMA and GBL in binary mixed solvents has been observed in terms of ion-ion, ion-solvent and
solvent-solvent interactions.