Potentiometric Determination of Silver Thiolate Formation Constants Using a Ag2S Electrode

Formation constants for silver thiolates were obtained by titration of the ligand in a constant temperature, ionic strength and pH medium and measuring the potential change at a Ag2S electrode. A non-linear equation was derived from which the first and second silver formation constants, 1 and 2, and the sulfide group acid dissociation constant, Ka, were determined. An overall estimate of the uncertainty in the derived parameters was obtained using a Monte Carlo approach. The procedure was compared to a previous work on AgHS°. Log 1, log 2 and - log Ka results were obtained for cysteine (11.9 ± 0.5, 15.2 ± 0.4, 7.8 ± 0.1), glutathione (12.3 ± 0.3, 14.3 ± 0.8, 8.8 ± 0.3) and 3-mercaptopropanoic acid (12.0± 0.4, 14.0 ± 0.4, 10.5 ± 0.3) at 20 °C and 0.01 m ionic strength.