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A new highly selective silver(I) electrode was prepared with a PVC membrane using 5,10,15-tris(pentafluorophenyl)corrole as an electroactive material, 2-nitrophenyl octyl ether (
o-NPOE) as a plasticizer and sodium tetraphenylborate (NaTPB) as an additive in the percentage ratio of 3:3:62:32 (corrole:NaTPB:
o-NPOE:PVC, w:w). The electrode exhibited linear response with a near Nernstian slope of 54.8
mV/decade within the concentration range of 5.1
×
10
−6 to 1.0
×
10
−1
M silver ions, with a working pH range from 4.0 to 8.0, and a fast response time of <30
s. Selectivity coefficients for Ag(I) relative to a number of interfering ions were investigated. The electrode is highly selective for Ag(I) ions over a large number of mono-, bi-, and tri-valent cations. Common interferents like Hg
2+ and Cd
2+ show very low interfering effect on the silver assay, which is valuable property of the proposed electrode. Several electroactive materials and solvent mediators have been compared and the experimental conditions were optimized. The sensor was applied to the determination of silver in real ore samples with satisfied results.