Extremely high electric field strengths in non-aqueous capillary electrophoresis

The influence of high electric field strength on the separation of basic analytes in non-aqueous alcohol background electrolyte (BGE) solutions was investigated. Increasing the separation voltage in capillary electrophoresis (CE) may be advantageous if the conductivity of the BGE solution is low enough to allow fast separations without excessive Joule heating or band broadening. The voltage range tested was 20-60 kV with methanol and ethanol, and 25-60 kV with propanol and butanol as solvent for BGE. The resulting electric field strengths ranged from 660 V cm(-1) to 2000 V cm(-1). Experiments were made with a special laboratory constructed CE: instrument. The separation efficiency vs. voltage curve was found to vary with the alcohol BGE solution. The increase in voltage decreased the separation efficiency in the case of methanol BGE solution. but with the other BGEs a clear efficiency maximum was obtained above 30 kV. The highest separation efficiencies were achieved with propanol BGE solution, where the efficiency maximum was reached at 45 kV However, reasonable efficiency was achieved even at 60 kV. The extent of Joule heating was determined by calculating the temperature inside the capillary and the observed plate heights were interpreted in terms of the Van Deemter equation. The decrease in the separation efficiency with higher voltage was attributed mainly to Joule heating in the case of methanol and ethanol BGE solution and to the analyte adsorption on the capillary wall with propanol and butanol BGE solutions. (C) 2001 Elsevier Science B.V. All rights reserved.