Pseudorotation effects in polarimetric detectors for HPLC are investig
ated, and a method to actively reduce these distortions is presented.
In this method, the refractive index of the eluents is maintained at a
constant value by mixing a variable amount of a second, optically den
ser phase. To do this, a detector measures the refractive index of the
eluents and its signal is fed back to control the pumping rate of the
second phase. To demonstrate the method, a prototype instrument using
a refractive index detector with a detection volume of 0.1 mu L was c
onstructed. It had a total dead volume of 3 mu L and made possible the
suppression of refractive index peaks as small as 60 mu L. This instr
ument was used to improve the accuracy of a commercial polarimetric de
tector in the determination of the enantiomeric excess of (R,S)-1-phen
ylethanol samples by canceling the pseudorotation.