ABSTRACT

High-performance liquid chromatography (HPLC) with electrochemical detection (ED) is used for the determination of electroactive constituents in complex mixtures. This chapter provides a basic understanding of the principles of HPLC-ED. The signal current is the result of an electrochemical conversion of the electroactive analyte by oxidation or reduction at the working electrode surface at an applied potential. Unless a mobile phase is less conductive, various modes of HPLC with ED can be used for the analysis of electroactive substances. Reverse-phase chromatography and ion-exchange chromatography are frequently utilized for determination of small organic molecules. The power spectral analysis of baseline noise in chromatographic data obtained using two types of pumps, reciprocating and syringe pumps. Various types of electrochemical flow cells have been developed and utilized for ED detectors. Carbon is the most common working electrode material for the electrochemical detectors. Cyclic voltammetry is useful for observing redox behavior of an interesting analyte over a wide potential range using simple electrochemical equipment.