Volumetric studies of solvation of carboxylic acids in aqueous, carbon tetrachloride, methanolic and methanolic-urea binary solutions at 298.15 K

Abstract

Abstract Experimental measurements of density property at 298.15 K for aqueous, carbon tetrachloride, methanolic, and 3.0004 mol·kg−1 urea in methanol as solvent systems for binary solutions of carboxylic acids (propionic acid, n-butyric acid, n-valeric acid and n-caproic acid) are reported. The data of density are used to obtain apparent molar volume of acids at the finite concentrations of solute (Vϕ) which were appropriately extrapolated to infinitely dilute concentration of acid to obtain the limiting apparent molar volumes (Vϕ0). The calculations of volume changes due to dimerization equilibria (in carbon tetrachloride and aqueous solutions) are made and used to study the volume changes due to dimerization of acid molecules. The results of Vϕ in methanol-urea solvent system are explained on the basis of channel-like structure-formation for the species (urea and acid molecules) in solution phase. The negative volume changes observed in case of aqueous solutions are explained on the basis of hydrophobic hydration while the same in carbon tetrachloride solutions occurring with positive volume changes are interpreted in terms of hydrogen-bonded dimer formation equilibria. The Vϕ variation with acid concentrations has been explained on the basis of solute-solvent interactions foe studied acids in methanol while in aqueous solutions, the same has been attributed to ionization (limiting concentration range), hydrogen bonding and hydrophobic interactions.