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Ultrasonic velocities and densities of binary mixtures of acetonitrile (AN) and n-butyronitrile (n-BTN) with Bu 4 NBPh 4 , Bu 4  NClO 4 , Bu 4  NI, Bu 4 NBr, Pr 4 NBr, Et 4 NI, Et 4 NBPh 4 , NaBPh 4 , NaClO 4  and CuClO 4  have been measured in the concentration range 0.0045 - 0.2 mol kg −1  over the entire composition range at 298.15 K. Isentropic compressibilities (Ks) and apparent molal isentropic compressibilities (Ks,ø ) have been calculated. Limiting apparent molal isentropic compressibilities (K o  s ,ø ) have been evaluated and split into the contribution of individual ions, i. e. into (K o  s ,ø )± values. (K o  s ,ø )± for Cu + , Na +  and Br −  in all cases is negative and large, for Bu 4 N +  and Ph 4 B −  positive and large, and for I −  and ClO 4  −  negative only in AN, and becomes positive in binary mixtures of AN and n-BTN for all compositions. The negative (K o  s ,ø )± values for Cu + , Na +  and Br −  indicate strong ionsolvent interactions involving electrostatic ion-dipole interactions. The large and positive (K o  s ,ø )± values for Bu 4 N +  and Ph 4 B −  show some special type of ion-solvent interactions (hydrophobic or dispersion interactions) with AN and n-BTN. The small negative value changing to a small positive value for I −  and ClO 4  − indicates the change of a weak electrostatic ion-solvent interaction to another weak special interaction. A comparison of (K o  s ,ø )± for Cu +  in some solvent systems shows that the ion-solvent interaction behaviour of Cu +  in AN +  n-BTN is similar to that in AN +  NM, AN +  TEP, BN +  TEP and PY + TEP mixtures but differs from that observed in AN+DMF and AN+DMSO mixtures.

zeitschrift für naturforschung a

Ion-Solvent Interactions Investigated by Isentropic Compressibility Measurements of Tetraalkylammonium, Copper(I) and Sodium Salts in Binary Mixtures of Acetonitrile and n-Butyronitrile at 298.15 K