The principle cause for lower plate numbers in capillary zone electrophoresis with most organic solvents.

Abstract

With longitudinal diffusion as an unavoidable source of peak broadening, the peak efficiency (expressed by the plate number, N) in capillary zone electrophoresis depends on the ratio of electrophoretic mobility, mu, and tracer- or self-diffusion coefficient, D. Both parameters are functions of the ionic strength of the electrolyte solution. According to theory, the mobility is decreased with increasing ionic strength by the relaxation effect (depending on the relative permittivity) and the electrophoretic effect (depending on the relative permittivity and the viscosity of the solvent), whereas the diffusion coefficient is decreased only by the relaxation effect. This allows the theoretical predictions that the plate number, which is proportional to the ratio mu/D, decreases with increasing ionic strength and that the magnitude of this reduction depends on the solvent. Taking the values for relative permittivity and viscosity allows forecasting that, in general, water as a solvent exhibits the smallest lowering of the plate number, as compared to organic solvents. The theoretical predictions are confirmed by the data for the ratio calculated from measured mobilities and diffusion coefficients for iodide as the analyte ion in water, methanol, and acetonitrile with ionic strength of the background electrolyte varying between 0.005 and 0.080 mol L(-1). Whereas the experimentally observed plate number per volt is reduced from its "ultimate value" of about 20 (analyte charge number z = 1, zero ionic strength) in water by only 10%, the decrease at the same ionic strength in methanol and acetonitrile reaches 25 to 30%. Thus, the maximum plate number should read Nmax approximately equals 13 zU (with U being the effective voltage) for these solvents with ionic strengths normally applied in capillary electrophoresis. This reduction is not stemming from inappropriate experimental conditions, but has fundamental physicochemical causes.