Enthalpies of transfer of tetraalkylammonium bromides and CsBr from water to aqueous DMF at 298.15 K

Enthalpies of transfer of tetraalkylammonium bromides and CsBr from water to aqueous DMF mixtures are reported and analyzed in terms of a new solvation theory. It was found that a previous equation could not reproduce these data over the whole range of solvent compositions. Using a new solvation theory to model the enthalpies of transfer shows excellent agreement between experimental and calculated values over the entire range of solvent compositions. The analyses show that tetrapropylammonium bromide, Pr4NBr, and tetrapentylammonium bromide, Pen(4)NBr, are preferentially solvated by water; in contrast tetrabutylammonium bromide, Bu4NBr, is preferentially solvated by DMF. The solvation of tetramethylammonium bromide, Me4NBr, and cesium bromide, CsBr, is random. The extent to which the tetraalkylammonium bromides disrupt solvent-solvent bonds increases systematically in going from Me4NBr to Pen(4)NBr.