A general approach to the derivation of peak area flow dependence in FIA and HPLC amperometric detection

P. Agrafiotou, C. Maliakas, A. Pappa-Louisi, S. Sotiropoulos*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

4 Scopus citations

Abstract

The dependence of the peak area, Q, on the analyte volumetric flow rate, U, in flow injection analysis (FIA) and high performance liquid chromatography (HPLC) with amperometric detection, was studied for typical electroactive species and in a wide flow rate range. Based on the hydrodynamics of thin channel flow cells (as established by steady state experiments) and simple dispersion theory considerations, a linear relationship between log Q and log U with a -2/3 slope has been derived in a general manner (irrespective to the type of dispersion) for amperometric detectors operated in the limiting current potential region. In the case of mixed mass transfer and kinetic control the variation of Q with U is more complicated but the peak area is still smoothly decreasing with the flow rate. These predictions were found to be in reasonable agreement with experiment for a few indicative systems both in FIA and HPLC experiments. On the contrary, the non-steady state current corresponding to the peak maximum of FIA and HPLC exhibited local maxima and the former could not be described by any of the equations proposed for the dispersion in FIA experiments. The practical implications of the form of integrated signal, Q, dependence on flow rate for FIA and HPLC amperometric detection are also discussed.

Original languageEnglish (US)
Pages (from-to)2447-2462
Number of pages16
JournalElectrochimica Acta
Volume48
Issue number17
DOIs
StatePublished - Jul 15 2003
Externally publishedYes

Keywords

  • Electrochemical detection
  • FIA
  • Flow rate
  • HPLC

ASJC Scopus subject areas

  • Chemical Engineering(all)
  • Electrochemistry

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