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Related Experiment Videos

Direct potentiometric information on total ionic concentrations.

A Ceresa1, E Pretsch, E Bakker

  • 1Department of Organic Chemistry, Swiss Federal Institute of Technology (ETH), Zürich.

Analytical Chemistry
|May 18, 2000
PubMed
Summary
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Polymeric membrane ion-selective electrodes show a super-Nernstian response due to boundary layer effects. This method, using labile complexes, allows distinguishing samples based on total ion concentration, even at fixed free ion levels.

Area of Science:

  • Electrochemistry
  • Analytical Chemistry
  • Materials Science

Background:

  • Polymeric membrane ion-selective electrodes (ISEs) can display non-ideal responses.
  • Aqueous boundary layers near the membrane limit ion flux, affecting electrode performance.
  • Inner solutions can induce fluxes that influence the observed electrode potential.

Purpose of the Study:

  • To investigate the super-Nernstian response of ISEs at low sample activities.
  • To explore the role of inner solutions and labile complexes in electrode behavior.
  • To develop ISEs capable of distinguishing samples based on total ion concentration.

Main Methods:

  • Utilized polymeric membrane ion-selective electrodes with specific inner solutions.
  • Employed the ionophore N,N-dicyclohexyl-N',N'-dioctadecyl-3-oxapentanediamide (ETH 5234) for calcium selectivity.

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  • Investigated the electrode response in the presence of labile calcium complexes and EDTA buffering.

    • Main Results:

    • Observed an apparently super-Nernstian response at low sample activities.
    • Demonstrated that labile complexes increase effective ion flux, making emf dependent on total ion concentration.
    • Successfully distinguished samples with varying total calcium but constant free calcium concentration (5 x 10(-8) M).

    Conclusions:

    • The super-Nernstian response is attributed to limited ion fluxes in the aqueous boundary layer.
    • ISEs can be designed to respond to total ion concentration by incorporating labile complexes.
    • This approach enables differentiation of samples with identical free ion concentrations but different total concentrations.