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Compressibility studies of aqueous and CCl4solutions of 18-crown-6 atT = 298.15 K

The Journal of Chemical Thermodynamics
Publication Date
DOI: 10.1016/j.jct.2005.04.005
  • 18-Crown-6
  • Isentropic And Isothermal Compressibilities
  • Transfer Compressibility
  • Hydration Number
  • Internal Pressure
  • Mathematics


Abstract The experimental measurements of sound velocities of 18-crown-6 (18C6) in dilute aqueous as well as in dilute CCl 4 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 ( ϕ K S , ϕ K T ) of 18C6 in solutions as well as the parameter energy volume coefficient ( δU/ δV) 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 ϕ K S 0 and h values are obtained as −17 mm 3 · MPa −1 · mol −1 and ∼4, respectively. The hydration number for 18C6 is found to be ∼2 when isothermal compressibility data ( ϕ K T 0 = - 8 mm 3 · MPa - 1 · mol - 1 ) are used. These observations have been explained on the basis of occupation of crown cavity by four water molecules, two of them (bridged) are firmly held while the other two are exchangeable. The corresponding studies in CCl 4 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 in CCl 4 solutions.

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