Chemometric investigation of complex equilibria in solution phase II: Sensitivity of chemical models for the interaction of AADH and FAH with Ni(II) in aqueous medium.

A detailed study of the species formed in the complex equilibria involving adipic acid dihydrazide (AADH)/2-furoic acid hydrazide (FAH) with Ni(II) using pH titration with glass electrode is performed. The results of modeling studies and effect of errors on the equilibrium constants of AADH/FAH with Ni(II) refined by the non-linear least squares program MINIQUAD75 are reported. Based on the expert system approach developed in our laboratory for the species formed from secondary formation data (n and n (H)), several preliminary chemical models were tested. For the four species identified (MLH, ML, ML(2)H, ML(2)), an exhaustive search of a different combination of models (15) was performed. Then other suspected minor species (ML(2)H(2), ML(3) and ML(3)H) were tested. The final best fit chemical model was found to contain ML(3)H to an extent of 3% along with the other four major species. In order to ascertain the accuracy of the stability constants and consequently distribution of the species, a detailed error analysis is attempted. As the existing least squares procedures cannot suppress the systematic errors, three-dimensional plots of the simultaneous effects of pH and TLO:TMO (1.5:1 to 5:1) on the percentage of species are drawn which are of immense use in arriving at optimum conditions for the preparation of a complex of definite stoichiometry.