POLAROGRAPHY AND STRIPPING VOLTAMMETRY OF METAL POLYCARBOXYLATE COMPLEXES - COMPLEXES OF CADMIUM AND ZINC WITH POLYACRYLIC AND POLYMETHACRYLIC ACIDS

Complex formation of Zn(II) and Cd(II) with polymethacrylic acid (PMA) and polyacrylic acid (PAA) is studied by sampled direct current, normal pulse, reverse pulse, and differential pulse polarography and by differential pulse anodic stripping voltammetry (DPASV). Titrations of Zn(II) or Cd(II) with partially neutralized PMA or PAA by DPASV allow the precise determination of the apparent formation constant K of the four systems. The two Zn(II) systems appear to be labile on the different time scales of the several techniques, without remarkable complications due to secondary phenomena. Their K values, determined by all techniques, agree satisfactorily. The two Cd(II) systems, and especially the Cd/PAA system, show rather involved behavior, which tends to normality when the degree of neutralization alpha-n of the polycarboxylates increases. Both slow kinetics and ligand adsorption coupled with induced Cd(II) adsorption (evidenced by maxima on the normal pulse polarograms) seem to be present. For all alpha-n values, DPASV yields higher estimates of K than do polarographic techniques.