The application of a supplementary potential at the end of a separatio
n capillary has been evaluated for the introduction of a reagent solut
ion for postcapillary reaction detection. Analyte zones emerging from
the capillary were introduced into a short (similar to 2 cm) reaction
capillary that was aligned with the separation capillary. The efficien
cy of transfer of the analyte zones to the reaction capillary and the
relative flow of reagent solution and separation electrolyte into the
reaction capillary were a function of the applied potential at the int
ersection of the two capillaries. Capillaries having i.d. values of 75
, 50, and 25 mu m were investigated. When a 2 cm X 25 mu m i.d. reacti
on capillary was added to a 60 cm X 25 mu m i.d. separation capillary,
the change in peak dispersion for the transfer of nitrite peaks acros
s the gap and through the reaction capillary was small (decrease from
420 000 to 400 000 theoretical plates) when the percent flow from the
reagent reservoir was 30% of the total combined flow. The influence of
displacement between the capillaries on peak transfer was similar for
both axial and vertical directions over the range of 1-50 mu m. A pot
ential application examined for this detection system was the addition
of a 0.4 mol/L strong base solution to permit the electrochemical det
ection of carbohydrates separated in a berate buffer system.