Analytical Sciences

Flow-Injection Potentiometry by Poly(vinyl chloride)-Membrane Electrodes with Diphosphoryl-dicarboxylicacid-p-tert-butylcalix[4]arene Ionophore for the Determination of Th(IV) Ions

Farhang MIZANI,*1 Mojtaba SHAMSIPUR,*2 Mohammad R. YAFTIAN,*3 and Dominique MATT*4

*1 Department of Chemistry, Faculty of Science, Payame-noor University, Iran
*2 Department of Chemistry, Faculty of Science, Razi University, Kermanshah, Iran
*3 Phase Equilibria Research Laboratory, Department of Chemistry, Faculty of Science, Zanjan University, Zanjan, Iran
*4 Chimie Inorganique Moléculaire Laboratory, Louis Pasteur University, Strasbourg, France

A new coated ion-selective electrode for the determination of trace thorium ions by flow-injection potentiometry (FIP) has been developed. A poly(vinyl chloride) (PVC)-based membrane was coated on a graphite electrode. The optimum membrane contained 5 wt% diphosphoryl-dicarboxylicacid-p-tert-butylcalix[4]arene (L) as the ionophore, 59 wt% dioctyl phthalate (DOP), 33 wt% PVC and 3 wt% additive sodium tetraphenylborate. The response was linear from 2.0 × 10⁻⁷ to 1.0 × 10⁻² M with a slope of 13.9 mV decade⁻¹ and a limit of detection of 9.0 × 10⁻⁸ M. The pH-independent region ranged from 3.15 to 6.5, and the lifetime was longer than 8 weeks when used in the flow injection analysis (FIA) system. Selectivity coefficients for several ions were obtained by the separate solutions method. Results showed that, for all cations used, the selectivity coefficients were in the order of 10⁻³, or smaller. The flow cell is simple to construct and free from memory effect problems over long periods of use. The proposed sensor was successfully applied to the direct determination of thorium in both real and synthetic samples.

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