Isothermal compressibility and internal pressure studies of some non-electrolytes in aqueous solutions at low temperatures

The experimental data of density (rho) and sound velocity (u) in the temperature range (275.15 to 293.15) K have been obtained for the systems (dioxane + water), (dimethylformamide + water), (tetrahydrofuran + water), and (acetonitrile + water). The specific heat (C-p) data for the above systems have been obtained at T = 279.15 K. The data obtained are used to calculate the derived parameters of adiabatic compressibility (beta(s)), at T = 275.15 K to T = 283.15 K, isothermal compressibility (beta(T)), and internal pressure (P-i) at T = 279.15 K for different concentrations. The solute properties: apparent molar volume (phi(V)), apparent molar expansivity (phi(E)), and apparent molar compressibility (phi(KS)) have been studied and the limiting values for these properties are reported. The variation in apparent molar properties with concentration and the corresponding temperature and pressure effects are discussed in terms of hydrophobic hydration (-H bonding interaction) and hydrophobic interaction (non-polar group solute-solute association in water). It is noted that the internal pressure of solutions is quite insensitive in the region of solute-solute association, while its variation with concentration in the dilute region is sensitive in contrast to the aqueous alcohol solutions. The molecular interactions also exhibit individualistic behaviour and are much dependent on structural alterations in water structure. (c) 2006 Elsevier Ltd. All rights reserved.