Elsevier

Analytica Chimica Acta

Volume 440, Issue 2, 9 August 2001, Pages 81-87
Analytica Chimica Acta

Highly selective and sensitive copper(II) membrane coated graphite electrode based on a recently synthesized Schiff’s base

https://doi.org/10.1016/S0003-2670(01)01051-0Get rights and content

Abstract

A PVC membrane electrode based on bis-2-thiophenal propanediamine (TPDA) coated directly on graphite is described. The electrode exhibits a Nernstian response for Cu2+ over a very wide concentration range (1.0×10−1 to 6.0×10−8 M) with a detection limit of 3.0×10−8 M (2.56 ng ml−1). It has a fast response time and can be used for at least 2 months without any major deviation. The proposed sensor revealed very good selectivities for Cu2+ over a wide variety of other metal ions and could be used in the pH range of 3.0–7.0. It was successfully used for direct determination of copper in black tea and as an indicator electrode in potentiometric titration of copper ion.

Introduction

The increasing use of ion sensors in the field of environmental, agricultural, industrial and medicinal analysis is putting more and more pressure on analytical chemists to develop new sensors for the fast, accurate, reproducible and selective determination of various species.

Due to the vital importance of copper in many biological systems [1], [2] and industry [3], and the urgent need for a copper-selective electrode for potentiometric monitoring of Cu2+ in different industrial, medicinal and environmental samples, a variety of ion carriers have been used in the construction of copper(II) selective electrodes. These copper ion carriers include small size thiacrown ethers [4], [5], non-cyclic neutral ionophores containing dithiocarbamate groups [6], [7] and nitrogen atom [8], calix [4], arenes [9] and Schiff’s bases [10]. However, all of these copper sensors have one, two or in some cases, all of the following problems: (1) high detection limit, (2) narrow working concentration range and (3) serious interfering effect of cations such as Fe3+, Na+, Sr2+, Co2+, Ni2+, Cs+, K+, Hg2+, Ag+.

In this paper, we report a novel copper ion-selective electrode by using a new Schiff’s base bis-2-thiophenal propanediamine (TPDA) as an excellent neutral carrier for potentiometric monitoring of ultra trace amount of Cu2+ ion.

Section snippets

Reagents and materials

Reagent grade dibutyl phthalate (DBP), benzyl acetate (BA), acetophenone (AP), tetrahydrofuran (THF), high relative molecular weight PVC (average MW 66 000), oleic acid (OA), sodium tetraphenylborate (NaTPB) were purchased from Merck Chemical Company. Reagent grade nitrate salts of the cations used (all from Merck) were of the highest purity available and used without any further purification except for vacuum drying over P2O5. TPDA was synthesized and purified, as described elsewhere [11].

Stability of TPDA complexes

The existence of two donating sulfur atoms as well as two donating nitrogens in TPDA molecule was expected to increase both the stability and selectivity of its complexes with transition and heavy metal ions over other metal ions. Thus, in preliminary experiments, the complexation of TPDA with a number of transition and heavy metal ions was investigated conductometrically in acetonitrile solution at 25.0±0.1°C [17], [18], in order to obtain a clue about the stability and selectivity of

Conclusions

The graphite-coated membrane electrode, prepared with TPDA under optimal PVC-membrane ingredients, revealed a Nernstian response over a wide copper concentration range, very fast response time and selectivity over a large number of metal ions. A comparison between the response characteristics of the proposed potentiometric sensor and those of the previously recorded copper ion-selective electrodes [4], [5], [6], [7], [8], [9], [10] indicated that the presented sensor is invariably superior in

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