Capillary electrophoretic separations have been investigated for six contro
lled narcotic analgesic compounds having related structures. Owing to the s
imilar charge-to-mass ratios of these compounds, capillary zone electrophor
esis failed to provide a satisfactory separation, whereas a baseline-resolv
ed separation was achieved in 10 min using micellar electrokinetic chromato
graphy. Column efficiencies of 40 000-150 000 plates/m were obtained with a
50 cm long, 50 mu m inner diameter (ID) capillary using 50 mM sodium dodec
yl sulfate (SDS) in a 50 mM berate solution containing 12% isopropanol. In
contrast, separation of this mixture by capillary electrochromatography pro
ved to be significantly superior. The capillary was 15 cm long, with an ID
of 75 mu m, and was packed with 1.5 mu m nonporous octadecyl silica (ODS) p
articles. The mobile phase consisted of 80% 10 mM tris(hydroxymethyl)aminom
ethane (Tris) and 20% acetonitrile, and contained 5 mM SDS. A complete sepa
ration was obtained in 2.5 min with an efficiency of 250 000-500 000 plates
/m.