Kinetic method for the determination of trace amounts of copper(II) in water matrices by its catalytic effect on the oxidation of 1,5-diphenylcarbazide

Abstract The chemical reaction between Cu(II) and 1,5-diphenylcarbazide (DPC) is revised from an analytical perspective. It is shown that instead of a Cu–DPC complex, an oxygen mediated DPC oxidation to diphenylcarbazone (DPCO) is the main reaction involved where Cu(II) acts as catalyst. Therefore, the signal observed corresponds to the oxidation product DPCO. Under certain specific conditions a chelate complex between Cu(II) and DPCO can also be observed. Kinetic parameters of these reactions are calculated. These results set the basis for the development of analytical methodologies for the determination of Cu(II) at ultra-trace levels. Since the study of interferences revealed Mg(II) as the most serious, an optimised flow injection system which allows the in-lineelimination of Mg(II) is presented. The limit of detection (k = 3) calculated for 10 blank replicates is 0.05 μg L−1 (injection volume 20 μL), the analytical sensitivity equals 48 μg−1 L and the sample throughput is 120 h−1. Obtained results for Cu(II) determination in natural waters as well as the validation of the analytical methodology will be given and discussed.

[1]  R. W. Turkington,et al.  Spectrophotometric Determination of Ultramicro Amounts of Copper with 1,5-Diphenylcarbohydrazide , 1958 .

[2]  R. Pflaum,et al.  The Chromium-Diphenylcarbazide Reaction1 , 1956 .

[3]  G. Goode,et al.  The separation of copper, lead, cadmium and zinc from high purity uranium metal by ion exchange on cellulose phosphate and their determination by square wave polarography , 1962 .

[4]  C. J. Ranter,et al.  The purity of commercial diphenylcarbazone , 1970 .

[5]  E. V. Dalen,et al.  The reactions of diphenylcarbazide and diphenylcarbazone with cations : Part IV. Cations of Mn, Fe, Co, Ni, Cu, Zn, Cd, Sn And Pb , 1963 .

[6]  W. Dasler,et al.  Spectrophotometric Determination of Copper Following Extraction with 1,5-Diphenylcarbohydrazide in Benzene , 1960 .

[7]  J. Dean Analytical Chemistry Handbook , 1995 .

[8]  M. Ramírez-Silva,et al.  Kinetic and thermodynamic study of the behaviour of diphenylcarbazide in aqueous solution with pH. , 2003, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[9]  Johanna Smeyers-Verbeke,et al.  Handbook of Chemometrics and Qualimetrics: Part A , 1997 .

[10]  R. Frazier,et al.  Spectrophotometric Determination of Chloride in Sweat and Serum with Diphenylcarbazone , 1958 .

[11]  H. Geering,et al.  Extraction and stability constants of copper complexes of 1,5-diphenylcarbazone , 1966 .

[12]  S. Balt,et al.  The reactions of diphenylcarbazide and diphenylcarbazone with cations : Part V1. Extraction dissociation constants of the carbazone complexes , 1964 .

[13]  E. V. Dalen,et al.  The reactions of diphenylcarbazide and diphenylcarbazone with cations : Part II1. Extraction behaviour and spectra of the reagents , 1962 .

[14]  G. H. Ayres,et al.  Spectrophotometric determination of rhodium with sym-diphenylcarbazone , 1960 .