Compressibility studies of aqueous and CCl4 solutions of 18-crown-6 at T=298.15 K

The experimental measurements of sound velocities of 18-crown-6 (18C6) in dilute aqueous as well as in dilute CCl4 solutions at T = 298.15 K are reported and these data are combined with density, expansivity and specific heat data to yield isentropic and isothermal compressibility properties in solutions. The compressibility and expansivity data are further used to obtain apparent molar compressibility values (phi(KS), phi(KT)) of 18C6 in solutions as well as the parameter energy volume coefficient (delta U/delta V)(T) in both solvent media. The calculations of hydration number (h) in aqueous solutions are made following the method developed by Shiio et al. At infinite dilution the phi(o)(KS) and h values are obtained as -17 mm(3). Mpa(-1) . mol(-1) and similar to 4, respectively. The hydration number for 18C6 is found to be similar to 2 when isothermal compressibility data (phi(o)(KT) = -8 mm(3). MPa-1 . mol(-1)) are used. These observations have been explained oil the basis of occupation of crown cavity by four water molecules, two of thern (bridged) are firmly held while the other two are exchangeable. The corresponding studies in CCl4 Solutions provide further information about transfer compressibility of 18C6 Molecules and the effect due to conformational status of 18C6 as well as the solvent effect. It has been noted that the geometrical relaxational properties of C-i and C-s conformations contributes largely towards the isothermal compressibility behaviour exhibited ill CCl4 solutions. (C) 2005 Elsevier Ltd. All rights reserved.