Pérez de Benito, Joaquín F.Martínez Cereza, Guillem2019-01-292018-09-171089-5639https://hdl.handle.net/2445/127695The ligand sequential replacement on chromium(III)-aqua complexes by L-alanine in slightly acidic aqueous solutions (pH range: 3.55-5.61) has been kinetically followed by means of UV-Vis spectrophotometry. A two rate constant model has been applied to fit the absorbance-time data, corresponding to the formation (k1) and decay (k2) of an intermediate not reactive enough to be in steady state (long-lived intermediate). The kinetic orders of the amino acid were fractional (0.40 ± 0.03 for k1 and 0.40 ± 0.02 for k2). The two steps showed base catalysis, and the activation energies were 60 ± 3 (for k1) and 83 ± 6 (for k2) kJ mol-1. The rate constants for the coordination of the first L-alanine ligand followed the sequence CrOH2+ < Cr(OH)2+ < Cr(OH)3, Cr3+ being almost inactive. This suggests that the increase in the reaction rate with increasing pH was caused by the enhancement of the lability of the Cr(III)-aqua bonds induced by the presence of hydroxo ligands. The activation parameters for a series of ligand substitution on Cr(III)-aqua complexes by organic molecules yielded a statistically significant enthalpy-entropy linear plot with an isokinetic temperature of 296 ± 21 K.49 p.application/pdfeng(c) American Chemical Society , 2018CromCinètica químicaAminoàcidsChromiumChemical kineticsAmino acidsinfo:eu-repo/semantics/article6849822019-01-29info:eu-repo/semantics/openAccess30222935