Volumetric, Viscosity and Conductance Studies of Solute–Solute and Solute–Solvent Interactions of Some Alkali Metal Chlorides in Aqueous Citric Acid at Different Temperatures

Abstract

Abstract The present study aims for the structure-making and structure-breaking behavior of some electrolytes in aqueous citric acid solution. The density, viscosity and conductance of some alkali metal chlorides lithium chloride (LiCl), sodium chloride (NaCl) and potassium chloride (KCl) in 0.01 m aqueous citric acid have been measured in the concentration range 0.01–0.12 m at 303.15, 308.15, 313.15 and 318.15 K. From these measurements, molar volume, viscosity parameters and molar conductance have been deliberated. Debye Hückel limiting law is used for the assessment of the contributions of various types of solute–solvent interactions. Jones–Dole viscosity equation is used to calculate viscosity B-coefficient for these salts in aqueous citric acid, which is known to provide information concerning the solvation of ions and their effects on the structure of the solvent in the near environment of the solute particles. The free energies of activation of viscous flow per mole of solvent, Δ μ 1 0 ‡ $\Delta \mu _1^{0\ddagger }$ and solute, Δ μ 2 0 ‡ , $\Delta \mu _2^{0\ddagger },$ have also been evaluated by using viscosity data. Using molar volume, the transfer volume Фv o tr has also been computed. The structure making/ breaking behavior of LiCl, NaCl and KCl is inferred from the sign of second derivative of partial molar volume with respect to temperature at constant pressure (d2φv o/dT2)p, Temperature coefficient of B. dB/dT and temperature coefficient of Walden product i.e. d(Λm oηo)/dT values. It has been found from these studies that LiCl, NaCl and KCl behave as structure-breaker in 0.01 m aqueous citric acid solution. The results have been qualitatively used to explain the molecular interaction and structural changes between the components of these mixtures.