The Principle of Detailed Balancing, the Iron-Catalyzed Disproportionation of Hydrogen Peroxide, and the Fenton Reaction

2022 ◽  
Author(s):  
David M. Stanbury
Keyword(s):  
Hydrogen Peroxide ◽  
Fenton Reaction ◽  
Detailed Balancing

The iron-catalyzed disproportionation of H2O2 has been investigated for over a century, as has been its ability to induce the oxidation of other species present in the system (Fenton reaction)....

A Systematic DFT Study of Two Elementary Steps Involving Hydrogen Peroxide and the Hydroxyl Radical in the Fenton Reaction

2018 ◽  
Author(s):  
Danilo Carmona ◽  
David Contreras ◽  
Oscar A. Douglas-Gallardo ◽  
Stefan Vogt-Geisse ◽  
Pablo Jaque ◽  
...  
Keyword(s):  
Hydrogen Peroxide ◽  
Hydroxyl Radical ◽  
Ab Initio ◽  
Fenton Reaction ◽  
Basis Set ◽  
Basis Sets ◽  
Dft Methods ◽  
Elementary Steps ◽  
Oxygen Oxygen ◽  
Complete Basis Set

The Fenton reaction plays a central role in many chemical and biological processes and has various applications as e.g. water remediation. The reaction consists of the iron-catalyzed homolytic cleavage of the oxygen-oxygen bond in the hydrogen peroxide molecule and the reduction of the hydroxyl radical. Here, we study these two elementary steps with high-level ab-initio calculations at the complete basis set limit and address the performance of different DFT methods following a specific classification based on the Jacob´s ladder in combination with various Pople's basis sets. Ab-initio calculations at the complete basis set limit are in agreement to experimental reference data and identified a significant contribution of the electron correlation energy to the bond dissociation energy (BDE) of the oxygen-oxygen bond in hydrogen peroxide and the electron affinity (EA) of the hydroxyl radical. The studied DFT methods were able to reproduce the ab-initio reference values, although no functional was particularly better for both reactions. The inclusion of HF exchange in the DFT functionals lead in most cases to larger deviations, which might be related to the poor description of the two reactions by the HF method. Considering the computational cost, DFT methods provide better BDE and EA values than HF and post--HF methods with an almost MP2 or CCSD level of accuracy. However, no systematic general prediction of the error based on the employed functional could be established and no systematic improvement with increasing the size in the Pople's basis set was found, although for BDE values certain systematic basis set dependence was observed. Moreover, the quality of the hydrogen peroxide, hydroxyl radical and hydroxyl anion structures obtained from these functionals was compared to experimental reference data. In general, bond lengths were well reproduced and the error in the angles were between one and two degrees with some systematic trend with the basis sets. From our results we conclude that DFT methods present a computationally less expensive alternative to describe the two elementary steps of the Fenton reaction. However, choice of approximated functionals and basis sets must be carefully done and the provided benchmark allows a systematic validation of the electronic structure method to be employed

scholarly journals Killing of Bacillus Spores by Aqueous Dissolved Oxygen, Ascorbic Acid, and Copper Ions

2003 ◽  
Vol 69 (4) ◽  
pp. 2245-2252 ◽  
Author(s):  
J. B. Cross ◽  
R. P. Currier ◽  
D. J. Torraco ◽  
L. A. Vanderberg ◽  
G. L. Wagner ◽  
...  
Keyword(s):  
Hydrogen Peroxide ◽  
Ascorbic Acid ◽  
Dissolved Oxygen ◽  
Hydroxyl Radicals ◽  
Fenton Reaction ◽  
Copper Ions ◽  
Transition Metal Ions ◽  
Fenton Reagent ◽  
Bacillus Spores ◽  
Modified Fenton

ABSTRACT An approach to decontamination of biological endospores is discussed. Specifically, the performance of an aqueous modified Fenton reagent is examined. A modified Fenton reagent formulation of cupric chloride, ascorbic acid, and sodium chloride is shown to be an effective sporicide under aerobic conditions. The traditional Fenton reaction involves the conversion of hydrogen peroxide to hydroxyl radical by aqueous ionic catalysts such as the transition metal ions. Our modified Fenton reaction involves the conversion of aqueous dissolved oxygen to hydrogen peroxide by an ionic catalyst (Cu2+) and then subsequent conversion to hydroxyl radicals. Results are given for the modified Fenton reagent deactivating spores of Bacillus globigii. A biocidal mechanism is proposed that is consistent with our experimental results and independently derived information found in the literature. This mechanism requires diffusion of relatively benign species into the interior of the spore, where dissolved O2 is then converted through a series of reactions which ultimately produce hydroxyl radicals that perform the killing action.

Toxicity of iron and hydrogen peroxide: the Fenton reaction

1995 ◽  
Vol 82-83 ◽  
pp. 969-974 ◽  
Author(s):  
Christine C. Winterbourn
Keyword(s):  
Hydrogen Peroxide ◽  
Fenton Reaction

Optimal experimental design and artificial neural networks applied to the photochemically enhanced Fenton reaction

2001 ◽  
Vol 44 (5) ◽  
pp. 339-345 ◽  
Author(s):  
S. Göb ◽  
E. Oliveros ◽  
S.H. Bossmann ◽  
A.M. Braun ◽  
C.A.O. Nascimento ◽  
...  
Keyword(s):  
Neural Networks ◽  
Hydrogen Peroxide ◽  
Artificial Neural Networks ◽  
Fenton Reaction ◽  
Irradiation Time ◽  
Batch Reactor ◽  
Reaction System ◽  
Process Conditions ◽  
Minor Effect ◽  
Artificial Neural

Among advanced oxidation processes (AOPs), the photochemically enhanced Fenton reaction may be considered as one of the most efficient for the degradation of contaminants in industrial wastewater. This process involves a series of complex reactions. Therefore, an empirical model based on artificial neural networks has been developed for fitting the experimental data obtained in a laboratory batch reactor for the degradation of 2,4-dimethyl aniline (2,4-xylidine), chosen as a model pollutant. The model describes the evolution of the pollutant concentration during irradiation time as a function of the process conditions. It has been used for simulating the behavior of the reaction system in sensitivity studies aimed at optimizing the amounts of reactants employed in the process, an iron(III) salt and hydrogen peroxide, as well as the temperature. The results show that the process is most sensitive to the concentration of iron(III) salt and temperature, whereas the concentration of hydrogen peroxide has a minor effect.

Pulp Mill Effluent Treatment by Fenton-Type Reactions Catalyzed by Iron Complexes

1999 ◽  
Vol 40 (11-12) ◽  
pp. 351-355 ◽  
Author(s):  
Jaime Rodríguez ◽  
David Contreras ◽  
Carolina Parra ◽  
Juanita Freer ◽  
Jaime Baeza ◽  
...  
Keyword(s):  
Hydrogen Peroxide ◽  
Aqueous Solutions ◽  
Fenton Reaction ◽  
Pulp Mill ◽  
Effluent Treatment ◽  
Pulp Mill Effluent ◽  
Large Decrease ◽  
Dihydroxybenzoic Acid ◽  
Pulp Bleaching ◽  
Efficient Option

Fenton reaction, which involves hydrogen peroxide and ferrous ion, has been proposed as an efficient option for effluent treatment. In this work, the treatment of a pulp bleaching effluent using Fenton-type reactions assisted by either, 2,3-dihydroxybenzoic acid (2,3-DHBA), 3,4-dihydroxybenzoic acid (3,4-DHBA) and 1,2-dihydroxybenzene (CAT), were studied. The treatment was evaluated by the removal of adsorbable organochloride compounds (AOX) and toxicity. Furthermore, the degradation of 2-chlorophenol and 4-chlorophenol in aqueous solutions were carried out, separately. Increase in oxidative activities of Fenton-type reactions mediated by the dihydroxybenzenes (DHBs) were found. These activities enhancement were related with a higher production of activated species by Fe/DHBs/H2O2, as indicted by chemiluminesce. The large decrease in AOX values and toxicity of the treated bleaching effluent by DHBs at pH 4.0 and 7.0 showed that 2,3-DHBA enhanced the activity of the Fenton reaction. The use of 3,4-DHBA and CAT resulted in loss of efficiencies of Fenton reaction to effluent treatment but not to pure chlorophenol solutions. At pH 7.0 lower efficiencies than those at pH 4.0 were achieved.

scholarly journals Factors Contributing to Hydrogen Peroxide Resistance in Streptococcus pneumoniae Include Pyruvate Oxidase (SpxB) and Avoidance of the Toxic Effects of the Fenton Reaction

2003 ◽  
Vol 185 (23) ◽  
pp. 6815-6825 ◽  
Author(s):  
Christopher D. Pericone ◽  
Sunny Park ◽  
James A. Imlay ◽  
Jeffrey N. Weiser
Keyword(s):  
Hydrogen Peroxide ◽  
Streptococcus Pneumoniae ◽  
Fenton Reaction ◽  
Bacterial Species ◽  
Atp Depletion ◽  
Host Cells ◽  
Toxic Effects ◽  
Aerobic Growth ◽  
Pyruvate Oxidase ◽  
Cytotoxic Effects

ABSTRACT Aerobic growth of Streptococcus pneumoniae results in production of amounts of hydrogen peroxide (H2O2) that may exceed 1 mM in the surrounding media. H2O2 production by S. pneumoniae has been shown to kill or inhibit the growth of other respiratory tract flora, as well as to have cytotoxic effects on host cells and tissue. The mechanisms allowing S. pneumoniae, a catalase-deficient species, to survive endogenously generated concentrations of H2O2 that are sufficient to kill other bacterial species is unknown. In the present study, pyruvate oxidase (SpxB), the enzyme responsible for endogenous H2O2 production, was required for survival during exposure to high levels (20 mM) of exogenously added H2O2. Pretreatment with H2O2 did not increase H2O2 resistance in the mutant, suggesting that SpxB activity itself is required, rather than an H2O2-inducible pathway. SpxB mutants synthesized 85% less acetyl-phosphate, a potential source of ATP. During H2O2 exposure, ATP levels decreased more rapidly in spxB mutants than in wild-type cells, suggesting that the increased killing of spxB mutants was due to more rapid ATP depletion. Together, these data support the hypothesis that S. pneumoniae SpxB contributes to an H2O2-resistant energy source that maintains viability during oxidative stress. Thus, SpxB is required for resistance to the toxic by-product of its own activity. Although H2O2-dependent hydroxyl radical production and the intracellular concentration of free iron were similar to that of Escherichia coli, killing by H2O2 was unaffected by iron chelators, suggesting that S. pneumoniae has a novel mechanism to avoid the toxic effects of the Fenton reaction.

scholarly journals Optimization for the Determination of Hydrogen Peroxide in River Water Based on the Fenton Reaction with Terephthalate

2019 ◽  
Vol 68 (2) ◽  
pp. 125-131 ◽  
Author(s):  
Ryuta UEKI ◽  
Ryota KATO ◽  
Yoshitaka IMAIZUMI ◽  
Yoko IWAMOTO ◽  
Waqar A. JADOON ◽  
...  
Keyword(s):  
Hydrogen Peroxide ◽  
River Water ◽  
Fenton Reaction ◽  
Water Based

Characterization of effects of selected organic substances on decomposition of hydrogen peroxide during Fenton reaction

2004 ◽  
Vol 49 (4) ◽  
pp. 129-134 ◽  
Author(s):  
K.C. Namkung ◽  
A. Aris ◽  
P.N. Sharratt
Keyword(s):  
Experimental Data ◽  
Hydrogen Peroxide ◽  
Fenton Reaction ◽  
Reactive Black 5 ◽  
Organic Substances ◽  
Oxidation Model ◽  
Simulation Results ◽  
Good Agreement

This study aims to investigate the effects of selected organic substances on the degradation of hydrogen peroxide during the Fenton reaction. Since the presence of organic substances can strongly affect the mechanism of the Fenton reaction, the information on effects of organic substances on the reaction would be a vital guide to the success of its application to the destruction of organics in wastewater. Several organic compounds having different structures were selected as model pollutants: 4-chlorophenol, 1,4-dioxane, chloroform, a dye (reactive black-5), and EDTA. Oxidation of 4-chlorophenol and reactive black-5 resulted in enormously fast degradation of hydrogen peroxide, while others such as 1,4-dioxane and chloroform showed much slower degradation. These experimental data were compared to simulation results from a computational model based on a simple áOH-driven oxidation model. Modelling results for chloroform and 1,4-dioxane were in relatively good agreement with the experimental data, while those for 4-chlorophenol and reactive black-5 were very different from the experimental data. The results for EDTA showed a different trend to those for other compounds. From these results, classification of organic substances into several sub-groups was tried.

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