Micellar and Mixed-Micellar Effects on Alkaline Hydrolysis of tris(1,10–phenanthroline)iron(II): Kinetic Exploration

Abstract

The kinetics of alkaline hydrolysis of tris(1,10–phenanthroline)iron(II) has been studied in the presence of nonionic and mixed nonionic–ionic micellar media at 308 K. The effects of mixed-micellar environments of nonionic with ionic surfactants (C₁₂E₂₃/ATABs and C₁₂E₂₃/SDS) on the hydrolytic rate have been studied. The rate decreases monotonically with an increment of [C₁₂E₂₃]_T (total Brij 35 concentration) at constant [⁻OH]₀ and has been discussed with the pseudo-phase micellar model. The rate also decreases with [C₁₂E₂₃]_T at a continuous addition of ionic surfactants (ATABs and SDS). The observed rate constant k_obs follows the empirical relation: k_obs = (k₀ + θK [C₁₂E₂₃]_T)/(1 + K [C₁₂E₂₃]_T) (where θ and K are empirical constants). The values of θ remain unaffected, whereas K decreases nonlinearly with [ATABs]_T in a mixed C₁₂E₂₃−ATAB micellar system. But the k_obs in a mixed C₁₂E₂₃–SDS micellar system is much lower than that of the C₁₂E₂₃–ATAB system and do not comply with any micellar kinetic models.

GRAPHICAL ABSTRACT

Keywords:

• Alkaline hydrolysis
• ionic and nonionic surfactants
• kinetics
• mixed micelles
• tris(1,10-phen)Fe(II)

ACKNOWLEDGMENT

The authors are thankful to Dr S Das, Assistant Professor of Chemistry, Jadavpur University, for his sincere all-round help and helpful discussion.