Electrophoretic mobilities of large organic ions in nonaqueous solvents:: Determination by capillary electrophoresis in propylene carbonate, N,N-dimethylformamide, N,N,-dimethylacetamide, acetonitrile and methanol

The mobilities of the monocharged permanent tertraphenylphosphonium cation and tetraphenylborate anion are determined by capillary zone electrophoresis in different organic solvents as a function of the ionic strength, I, of the background electrolyte. The nonaqueous solvents are propylene carbonate (PC), N,N-dimethylformamide (DMF), N,N,-dimethylacetamide (DMA), acetonitrile (MeCN) and methanol (MeOH). The ionic strength is between 5 and 50 mmol/L. The mobility as a function of I is in good agreement with the theory of Debye, Hockel and Onsager (DHO), extended by the ion size parameter as introduced by Falkenhagen and Pitts. The values of the limiting DHO slopes of the mobility vs. I curves the slopes express the influence of the solvent on the reduction of the mobility with increase of decrease in the order MeCN > MeOH > DMF > DMA > PC. Absolute mobilities (obtained by extrapolation to I = 0) of a particular ion differ by a factor of about 7 between the solvents. However, constancy within 10% is observed for their Walden products (the absolute mobility multiplied with the solvent's macroviscosity). The role of dielectric friction on the mobility of the present monocharged, large analyte ions is discussed according to the theory of Hubbard and Onsager. Based on the radii of the ions, the static permittivity of the solvent and its permittivity at infinite frequency, and the relaxation time of polarization, an equal contribution of dielectric and hydrodynamic friction is predicted in MeOH as solvent. Experimental data are in contrast to this prediction, indicating the overestimation of dielectric friction, and the dominance of hydrodynamic friction on the migration of the analyte ions in all solvents under consideration.