Two Rate constant kinetic model for the chromium(III)-EDTA complexation reaction by numerical simulations

The complexation reaction of Cr(III) ion in the presence of a large excess of ethylenediaminetetraacetic acid (EDTA) does not follow a pseudo-first-order kinetics as sometimes suggested. There are two causes for the deviation from this simple behavior: the involvement of a long-lived intermediate, precluding the application of the steady-state approximation, and the autoinhibition provoked by the release of hydrogen ions from the organic ligand to the medium as the final Cr(III)-EDTA violet complex is formed. Numerical simulations have allowed obtaining for each kinetic experiment the values of two rate constants, k(1) (corresponding to the formation of the long-lived intermediate from the reactants) and k(2) (corresponding to the formation of the final complex product from the long-lived intermediate), as well as the number of hydrogens liberated per molecule of final complex product formed (H-kin). The results indicate that k(1) is associated with a fast step (E-a = 87 +/- 4 kJ mol(-1)) and k(2) to a slow step (E-a = 120 +/- 2 kJ mol(-1)), whereas the number of hydrogen ions lies within the range 0 < H-kin < 2 in all the kinetic runs. A mechanism in accordance with the experimental data has been proposed. (C) 2017 Wiley Periodicals, Inc.