Abstract
The apparent molal volumes ${\phi}_v$ of a series of homologous tetraalkylammonium chlorides, $Me_4NCl, Et_4NCl, Pr_4NCl,\;and\;Bu_4NCl$, in a series of isopropanol-water mixtures have been determined at $30^{\circ}C$ from precision density measurements using pycnometers. The values of ${\phi}_v$ extrapolated to infinite dilution give partial molal volumes $\={V}^{\circ}$s which are almost additive for successive homologues and enable one to determine the absolute individual ionic partial molal volumes. The experimental results are discussed in terrns of the varying size and surface charge of the ions and the structure of the binary solvent mixtures. The results indicate that at 0.1 mole fraction isopropanol the maximum structuredness of water causes a minimum in the tetraalkylammonium-cation partial molal volumes, while at 0.2 mole fraction the solvent structure is such that the free volumes is a minimum and the electrostrictive effect of chloride ion is a maximum.