Studies on ion-pair and triple-ion formation of some tetraalkylammonium salts in binary solvent mixtures of benzene and tetrahydrofuran at 298.15 K

Conductivities of some tetraalkylammonium halides, viz. tetrabutylammonium bromide (Bu4NBr), tetrapentylammonium bromide (Pen4NBr), tetrahexylammonium bromide (Hex4NBr) and tetraheptylammonium bromide (Hep4NBr) were measured at 298.15 K in THF + C6H6 mixtures with 10, 20, 30 and 40 mass% of C6H6. A minimum in the conductance values was observed as concentration increases, which dependent both on the salt and the solvent. The observed molar conductivities were explained by the formation of ion-pairs (M+ + X− ↔ MX, KP) and triple-ions (2 M+ + X− ↔ M2X+; M+ + 2X− ↔ MX2−, KT). A linear relationship between the triple-ion formation constants [log(KT/KP)] and the salt concentrations at the minimum conductivity (log Cmin) was given for all salts in C6H6 + THF mixtures. The formation of triple-ions might be attributed to the ion sizes in solutions in which coulombic interactions and covalent bonding forces act as the main forces between the ions (R4N+ ⋯ X−).