FeIII–TAML-catalyzed green oxidative degradation of the azodyeOrange II by H2O2and organic peroxides: products, toxicity, kinetics, and mechanisms

Abstract

Oxidation of Orange II ([4-[(2-hydroxynaphtyl)azo]benzenesulfonic acid], sodium salt) by hydrogen peroxide catalyzed by iron(III) complexed to tetra amido macrocyclic ligands (FeIII–TAML activators) in aqueous solutions at pH 9–11 leads to CO2, CO, phthalic acid and smaller aliphatic carboxylic acids as major mineralization products. The products are non-toxic according to the Daphnia magna test. Several organic intermediates have been identified by HPLC and GC-MS that allowed the detailed description of Orange II degradation. The catalytic oxidation can also be performed by organic oxidants such as benzoyl peroxide, tert-butyl and cumyl hydroperoxides. Kinetic studies of the catalyzed oxidation indicated that FeIII–TAML activators react first with ROOR′ to form an oxidized catalyst (kI), which then oxidizes Orange II (kII). Neglecting the reversibility of the first step, the rate equation is rate = kIkII[FeIII][ROOR′][Dye]/(kI[ROOR′] + kII[Dye]); here FeIII and ROOR′ represent the catalyst and peroxide, respectively. The rate constant kI equals (74 ± 3) × 103, (1.4 ± 0.1) × 103, 24 ± 2, and 11 ± 1 M−1 s−1 for benzoyl peroxide, H2O2, t-BuOOH, and cumyl hydroperoxide at pH 9 and 25 °C, respectively. An average value of kII equals (3.1 ± 0.9) × 104 M−1 s−1 under the same conditions. The unraveling of the kinetic mechanism allows the comprehension of the robust reactivity, and this is discussed in detail using the representative results of DFT calculations.