The 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 (k(1)) and decay (k(2)) 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 k(1) and 0.40 +/- 0.02 for k(2)). The two steps showed base catalysis, and the activation energies were 60 +/- 3 (for k,) and 83 6 (for k(2)) 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.