Physics and chemistry of lithium halides in 1,3-dioxolane and its binary mixtures with acetonitrile probed by conductometric, volumetric, viscometric, refractometric and acoustic study

Electrolytic conductance (Λ), density (ρ), viscosity (η), refractive index (nD) and ultrasonic speed (u) of lithium halides LiX (where X = Cl, Br, I) have been studied in different mass fraction (w1 = 0.00–0.75) of acetonitrile (ACN) + 1,3-dioxolane (1,3-DO) mixtures at 298.15 K. The limiting molar conductivity (Λ0), association constant (KA), and distance of closest approach of ions (R) have been evaluated using Fuoss-conductance equation (1978). The deviation of conductometric curve (Λ vs √c  ) from linearity in 1,3-DO, analyzed by the Fuoss–Kraus theory. The limiting apparent molar volume (ϕV0), experimental slope (SV*) derived from Masson equation, and viscosity B and A  -coefficients derived from Jones–Dole equation supplemented with density and viscosity data, respectively, have been interpreted in terms of ion–solvent and ion–ion interactions. The limiting partial molar adiabatic compressibility (ϕK0), have also been obtained from the value of ultrasonic speed (u) and discussed them to interpret the same.

► Lithium halide interaction in binary mixture of acetonitrile and 1,3-dioxolane.
► Triple-ion formation in 1,3-dioxolane.
► More ion–solvent interaction than ion–ion interaction in all the solvent mixture.
► Ion solvation is due to preferential solvation and dimerization of acetonitrile.