A very sensitive and selective catalytic adsorptive cathodic stripping procedure for trace measurements of cobalt is presented. The method is based on adsorptive accumulation of cobalt–CCA (calcon carboxylic acid) complex onto a hanging mercury drop electrode followed by reduction of the adsorbed species by voltammetric scan using differential pulse modulation. The reduction current is enhanced catalytically by nitrite. The effect of various parameters such as pH, concentration of CCA, concentration of nitrite, accumulation potential and accumulation time on the selectivity and sensitivity were studied. The optimum condition for the analysis of cobalt, include pH 5.2 (Acetate buffer), 2.1 μ M clacon carboxylic acid, 0.032 M sodium nitrite and an accumulation potential of 0.05 V (versus Ag/AgCl). Under these optimum conditions and for an accumulation time of 60 s, the measured peak current at –0.480 V is proportional to the concentration of cobalt over the entire concentration range tested 0.003–2.0 ng ml –1 with a detection limit of 1 pg ml –1 for an accumulation time of 60 s and 2.0–10.0 ng ml –1 for an accumulation time of 40 s. The relative standard deviations for ten replicate measurement of 0.5 ng ml –1 of cobalt were 3.1%. The main advantage of this new system is the microtrace Co(II) determination by ASV. The method was applied to determination of cobalt in a water sample and some analytical grade salts with satisfactory results.
