Selective electrochemical sensor for copper (II) ion based on chelating ionophores

Plasticized membranes using 3-(2-pyridinyl)-2H-pyrido[1,2,-a]-1,3,5-triazine-2,4(3H)-dithione (L1) and acetoacetanilide (L2) have been prepared and explored as Cu2+-selective sensors. Effect of various plasticizers, viz. chloronaphthalene (CN), benzyl acetate (BA), o-nitrophenyloctyl ether (o-NPOE), and anion excluders, sodium tetraphenylborate (NaTPB) and oleic acid (OA) was studied in detail and improved performance was observed at several instances. Optimum performance was observed with dithione derivative (L1) having a membrane composition of L1 (5):PVC (120):o-NPOE (240):OA (10). The sensor works satisfactorily in the concentration range 5.0 × 10−8 to 1.0 × 10−2 M (detection limit 4.0 × 10−8 M) with a Nernstian slope of 29.5 mV decade−1 of activity. Wide pH range (3.0–9.5), fast response time (12 s), non-aqueous tolerance (up to 20%) and adequate shelf life (4 months) indicate the vital utility of the proposed sensor. The potentiometric selectivity coefficient values as determined by match potential method (MPM) indicate good response for Cu2+ in presence of interfering ions. The proposed electrode comparatively shows good selectivity with respect to alkali, alkaline earth, transition and some rare earth metals ions. The electrode was used for the determination of copper in different milk powder, water samples and as indicator electrode in potentiometric titration of copper ion with EDTA.