The protonation and Ni(II) complexation of 4-(2-pyridylazo) resorcinol (PAR) in ionic strength 0.1 mol L⁻¹ KNO₃ at 25 ℃ has been studied by global analysis. In spectrophotometric titrations, linear or near-linear dependence of concentration profiles and the existence of minor species can cause difficulties in the evaluation of the data. Both calculated absorption spectra and the corresponding equilibrium constants are not or only poorly defined. The result is the inability to reliably fit a reasonable model to the data. In second order global analysis, a number of spectrophotometric titrations with different initial concentrations are simultaneously analyzed. In this way, conditions for the significant formation of all species can be obtained and consequently the concentration matrix is augmented to full rank. EQUISPEC is a computer program using the matrix based MATLAB environment for second order global analysis of spectrophotometric equilibrium data. The spectrophotometric titrations were carried out at least in four different metal to ligand ratios.
Journal of the Brazilian Chemical Society Vol. 18, Issue 2, p. 267-272