Recently, methods for controlling the bulk how of the buffer which are
independent of the electrophoretic migration have been demonstrated i
n capillary electrophoresis (CE) systems. These methods include contro
lling the electroosmosis by radially directed electric fields, and con
trolling the bulk flow by siphoning. This paper investigates basic dis
persion mechanisms at work by examining the dispersion of dimethyl sul
foxide under various external control methods. It is found that the el
ectroosmotic how control methods exhibit the same dispersive behavior
as the conventional CE system. In particular, the results for pH 7 buf
fers obey the theoretical expression for the plate height in all confi
gurations. However, in all configurations, pH 2.7 buffers do not follo
w the theory, and counter to intuition, additional pressure can improv
e the plate height at pH 2.7. Taking all these methods together, one c
an develop a technique to appropriately adjust the electrophoretic and
bulk how to optimize resolution.