Spectrophotometric determination of formation constants of various types of complexes by use of another competing ligand

A method has been developed for determining the formation constants of various colored complexes, ML and ML₂, and their protonated forms, spectrophotometrically, by measuring the absorbance of all forms of the colored complexes in the absence and presence of another ligand, Y, which forms the colorless complex MY, with a known formation constant. This method is based on the competition between the two ligands, L and Y, for the metal ion. An experimental test has been done for the Zn(II)-4-(2-pyridylazo)resorcinol (PAR) (H₂L) system by using nitrilotriacetic acid (NTA) as another ligand, Y. The results showed that the concentrations of PAR used were suitable for the study of 1:2 complexes, ZnL₂, ZnL(HL) and Zn(HL)₂, but were too high to study the 1:1 complexes. With the aid of the formation constants of ZnL and ZnHL determined previously, the experimental data gave an approximate value for the formation constant of ZnY (Y = NTA) which agreed with the published value.