The isentropic compressibilities (Ks) and apparent molal isentropic compressibilities (Ks,φ) of lithium
perchlorate (LiClO4), sodium perchlorate (NaClO4), sodium tetraphenylborate (NaBPh4),
tetrabutylammonium tetraphenylborate (Bu4NBPh4) and tetrabutylammonium perchlorate (Bu4NClO4),
have been calculated from measured ultrasonic velocity (u) and density (ρ) of these salts in the
concentration range 0.001 to 0.60 mol Kg-1 in the mixed binary solutions of nitromethane (NM) and
dimethyl sulfoxide (DMSO) containing 0, 20, 40, 60, 80 and 100 mol% of DMSO in NM at 298.15 K.
Limiting values of apparent molal isentropic compressibilities (K°s,φ) for various salts were evaluated
and split into the contributions (K°s,φ)± of the individual ions. Exceptionally large and negative (K°s,φ)±
values were obtained whose variation with solvent composition shows strong solvation of both Li+
and Na+ in NM + DMSO mixtures at all compositions of the mixed binary solutions. Solvation of Li+
and Na+ increases as mol% of DMSO in NM increases. Solvation exhibited by Li+, however, is much
stronger than Na+ in all compositions of the mixtures. Solvation exhibited by ClO4
– in NM + DMSO
mixtures is weak which perchlorate ion shows by having some interactions with DMSO in the
DMSO-rich compositions of the mixtures. The large and positive values for Bu4N+ and Ph4B– are
indicative of some special type of interactions, mainly solvophobic with the solvent molecules.