The effect of composition of solid silver amalgam electrodes on their electrochemical response

The main purpose of this work was to evaluate the effect of the silver to mercury ratio on the voltammetric responses of silver solid amalgam electrodes (AgSAE's). For this, the AgSAE were prepared by mechanical mixing the metals in the following mass ratios of silver to mercury: 30/70, 40/60, 50/50, 60/40, and 70/30. The resulting AgSAE's were physically characterized by energy dispersive X-ray analysis, X-ray diffraction and scanning electron microscopy, confirming the mass percentages of the silver and mercury, the total absence of liquid mercury and a globular structure of all AgSAE's. Furthermore, it was observed that the AgSAE 30/70 contained only one single phase (Ag2Hg3), and no metallic silver or mercury oxides. Additionally, the resulting AgSAE's were chemically characterized with respect to the influence of the electrode composition on the reproducibility and electrochemical signals of a hexamine-ruthenium (III) chloride solution by use of electrochemical impedance spectroscopy and cyclic voltammetry. The separation between anodic and cathodic peaks, and consequently, the charge transfer resistance across the electrode/solution interface, and the electroactive area were calculated demonstrating that the 30/70 composition is the best surface for practical applications. Finally, square-wave voltammetry experiments were performed in 4-nitrophenol solution, with a previous optimization of the experimental and voltammetric parameters. The calculated detection limit shows that the AgSAE 30/70 is suitable for determining any contamination by p-nitrophenol, minimizing the toxic residues in case of using liquid mercury electrodes.