Catalytic Decomposition of Hydrogen Peroxide by Fe(III) in Homogeneous Aqueous Solution: Mechanism and Kinetic Modeling

1999/07/02 by Joseph De Laat, J. De Laat, HervÉ Gallard +1 · 30 citations
Environmental Science · Chemistry · Energy · #Advanced oxidation water treatment #Electrochemical Analysis and Applications #Electrocatalysts for Energy Conversion

paper · doi:10.1021/es981171v

Abstract

This paper describes a kinetic model for the decomposition of hydrogen peroxide by ferric ion in homogeneous aqueous solution (pH < 3). The reaction was investigated experimentally at 25.0 °C and I = 0.1 M (HClO 4 /NaClO 4 ), in a completely mixed batch reactor and under a wide range of experimental conditions (1 ≤ pH ≤ 3; 0.2 mM ≤ [H 2 O 2 ] 0 ≤ 1 M; 50 μM ≤ [Fe(III)] 0 ≤ 1 mM; 1 ≤ [H 2 O 2 ] 0 /[Fe(III)] 0 ≤ 5000). The results of this study demonstrated that the rate of decomposition of hydrogen peroxide by Fe(III) could be predicted very accurately by a kinetic model which takes into account the rapid formation and the slower decomposition of Fe(III)−hydroperoxy complexes (Fe III (HO 2 ) 2+ and Fe III (OH)(HO 2 ) + ). The rate constant for the unimolecular decomposition of the Fe(III)−hydroperoxy complexes was determined to be 2.7 × 10 - 3 s - 1 . The use of the kinetic model allows a better understanding of the effects of operational parameters (i.e., pH and [H 2 O 2 ] 0 /[Fe(III)] 0 ) on the complex kinetics of decomposition of H 2 O 2 by Fe(III).

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