Abstract

TTHA gives an anodic d.c. wave and s.w. peak corresponding to oxidation of mercury at the d.m.e. surface with formation of a Hg(II)—TTHA complex. Similar processes are known for other ligands, e.g. EDTA and DCTA, but the greater stability of the Hg(II)—TTHA complex gives a significant improvement in the shapes of the anodic wave and s.w. peak. An increase in pH shifts the E 1 2 and E p values towards more negative values because the conditional stability constant of the Hg(II)—TTHA complex is increased. Although the half–wave potentials of the reduction wave of Hg(II)—TTHA and of the anodic wave of TTHA, are the same, other criteria for the reversibility of polarographic reactions suggest that the anodic TTHA process at the d.m.e. is not completely reversible. The temperature coefficient of the wave and s.w. peak as well as the dependence of the wave height on the square root of the mercury head prove that the process is diffusion–controlled. Supporting electrolytes are given for which the d.c. wave and the s.w. peak of TTHA are well-shaped, with linear dependence between the wave or peak height and the concentration of TTHA in the ranges 5 × 10 -5–5 × 10 -4 M (d.c.) and 1 0 -5–1 × 10 -4 M (s.w.).

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