title: Determination of electroosmotic flow in nonaqueous capillary electrophoresis.
abstract: Mobility of the electroosmotic flow (mu(EOF)) in fused-silica capillaries strongly depends on the nature of the background electrolyte. In this study, 27 solvent systems were investigated, namely water, methanol, ethanol, 2-propanol, 1-butanol, acetonitrile (MeCN), formamide, N-methylformamide (NMF), N,N-dimethylformamide and dimethyl sulfoxyde, as well as 8 hydroorganic and 9 organic mixtures. For each system, six mu(EOF) were determined at a different ionic strength in basic conditions, and an absolute electroosmotic flow mobility (mu(EOF,0)) was extrapolated according to the Debye-Huckel Onsager model. The obtained mu(EOF,0) values were correlated with the solvent's relative permittivity (epsilon) and viscosity (eta). A good correlation (r2=0.867) between mu(EOF,0) and the solvent's epsilon/eta ratio was demonstrated, except for two solvents (MeCN and NMF). Furthermore, the donor number (DN) of a solvent took into account the possible zeta potential modification in the electric double layer near the capillary wall. Consequently, the relationship between mu(EOF,0) and epsilon/(eta x DN) was superior, with a r2 of 0.943 for 10 pure solvents.
authors.affiliation: Laboratory of Pharmaceutical Analytical Chemistry, School of Pharmacy, University of Geneva, Boulevard d'Yvoy 20, 1211 Geneva 4, Switzerland.
authors.forename: Laurent
authors.initials: L
authors.lastname: Geiser
authors.forename: Myriam
authors.initials: M
authors.lastname: Mirgaldi
authors.forename: Jean-Luc
authors.initials: JL
authors.lastname: Veuthey
mesh_terms: D019075:Electrophoresis, Capillary / Q000379:methods*; D009995:Osmosis; D012997:Solvents / Q000737:chemistry*
chemical_list: D012997:Solvents