Are the asserted advantages of organic solvents in capillary electrophoresis real? A critical discussion.

Background electrolytes (BGEs) prepared in pure organic solvents are common alternatives to aqueous BGEs in capillary electrophoresis. Several general advantages of organic solvents over water have been asserted in the literature, namely (i) organic solvents increase the separation selectivity; (ii) organic solvents increase the separation efficiency; (iii) high separation voltages and/or high BGE ionic strengths can be used in organic solvents due to lower electric current compared to water. Related assumptions are that (iv) due to higher field strengths applicable in organic solvents the analysis time is shorter than in aqueous BGEs, and (v) the solubility and/or stability of components (either analytes or BGE chemicals) is higher/better in organic solvents. In the present work, these asserted advantages were critically evaluated based on the physical principles of ion transport and zone dispersion in solution. The result was that many of the above-mentioned general advantages are overestimated or even inexistent; often they have no fundamental basis.