Investigation of mercury-free potentiometric stripping analysis and the influence of mercury in the analysis of trace-elements lead and zinc

Application of Potentiometric Stripping Analysis (PSA), without any mercury, to determination of trace-elements lead and zinc, results in linear responses between stripping-peak areas and concentrations within the range 0-2000 ng/g. The best response, as determined by the size of stripping areas, was obtained with an electrode prepared with mercury but without mercury ions in the electrolyte. In 0.09-0.1 M HCl lead is analysed by a freshly polished glassy-carbon electrode while analysis of zinc requires an electrode activation procedure. The electrode activation is performed by stripping zinc in an electrolyte containing 0.1 M HCl and 2 mg/g Zn2+ and electrolysis at -1400 mV(SCE). It is suggested that the concentration range of linear response occur where the electrode is not fully covered by metal clusters during the electrolysis step. The influence of mercury is investigated and a model is proposed which explains the co-deposition of mercury and test metals in the electrolysis step in terms of a charge-distribution parameter. The model explains that the decrease of stripping peak area, as a function of concentration, is entirely due to mercury ions being simultaneously reduced together with the ions of the test metal in the electrolysis step. The influence of hydrogen evolution and oxygen reduction together with possible improvements of the method are discussed.