Detection of Radicals Generated by Strong Oxidants in Acidic Media

Holzforschung ◽  
1999 ◽  
Vol 53 (3) ◽  
pp. 285-291 ◽  
Author(s):  
M. Ragnar ◽  
T. Eriksson ◽  
T. Reitberger
Keyword(s):  
Aqueous Solution ◽  
Hydrogen Peroxide ◽  
Hydroxyl Radical ◽  
Hydroxyl Radicals ◽  
Second Step ◽  
Stopped Flow ◽  
Acidic Media ◽  
Ph Range ◽  
Acidic Hydrogen ◽  
Ozone Bleaching

Summary A new method to study superoxide and hydroxyl radicals in aqueous solution in the pH range 1 to 6 is described and critically evaluated. The method primarily detects superoxide, which reacts with tetranitromethane (TNM) by reductive cleavage. The strongly coloured nitroform anion (ε350nm = 15000M−1 cm−1) formed, is easily measured in a spectrophotometer or in a stopped-flow equipment. Hydroxyl radicals are measured indirectly. In a first step the hydroxyl radical reacts with iso-propyl alcohol to give acetone and superoxide. The superoxide formed is then in a second step detected with TNM. The TNM-method was primarily designed to monitor the radical formation under ozone bleaching conditions, but it is also applicable in acidic hydrogen peroxide.

Heterogeneous Fenton Catalytic Removal of Organic Pollutant in Aqueous Solution by using Coal Gangue as a Catalyst

2019 ◽  
Vol 12 (4) ◽  
pp. 312-325
Author(s):  
Jiwei Zhang ◽  
Jingjing Xu ◽  
Shuaixia Liu ◽  
Baoxiang Gu ◽  
Feng Chen ◽  
...  
Keyword(s):  
Aqueous Solution ◽  
Hydrogen Peroxide ◽  
Hydroxyl Radical ◽  
Removal Rate ◽  
Organic Pollutant ◽  
Coal Gangue ◽  
Ion Leakage ◽  
Heterogeneous Fenton ◽  
Solution Ph ◽  
X Ray

Background: Coal gangue was used as a catalyst in heterogeneous Fenton process for the degradation of azo dye and phenol. The influencing factors, such as solution pH gangue concentration and hydrogen peroxide dosage were investigated, and the reaction mechanism between coal gangue and hydrogen peroxide was also discussed. Methods: Experimental results showed that coal gangue has the ability to activate hydrogen peroxide to degrade environmental pollutants in aqueous solution. Under optimal conditions, after 60 minutes of treatment, more than 90.57% of reactive red dye was removed, and the removal efficiency of Chemical Oxygen Demand (COD) up to 72.83%. Results: Both hydroxyl radical and superoxide radical anion participated in the degradation of organic pollutant but hydroxyl radical predominated. Stability tests for coal gangue were also carried out via the continuous degradation experiment and ion leakage analysis. After five times continuous degradation, dye removal rate decreased slightly and the leached Fe was still at very low level (2.24-3.02 mg L-1). The results of Scanning Electron Microscope (SEM), energy dispersive X-Ray Spectrometer (EDS) and X-Ray Powder Diffraction (XRD) indicated that coal gangue catalyst is stable after five times continuous reuse. Conclusion: The progress in this research suggested that coal gangue is a potential nature catalyst for the efficient degradation of organic pollutant in water and wastewater via the Fenton reaction.

Formation of Hydroxyl Radicals from Hydrogen Peroxide and Iron Salts by Superoxide- and Ascorbate-Dependent Mechanisms: Relevance to the Pathology of Rheumatoid Disease

1983 ◽  
Vol 64 (6) ◽  
pp. 649-653 ◽  
Author(s):  
D. A. Rowley ◽  
B. Halliwell
Keyword(s):  
Hydrogen Peroxide ◽  
Hydroxyl Radical ◽  
Hydroxyl Radicals ◽  
Oxygen Radicals ◽  
Rheumatoid Disease ◽  
Iron Salts ◽  
Low Concentrations ◽  
Short Period ◽  
Generating System

1. Superoxide and hydrogen peroxide are formed by activated phagocytes and react together in the presence of iron salts to form the hydroxyl radical, which attacks hyaluronic acid. Ascorbic acid also interacts with hydrogen peroxide and iron salts to form hydroxyl radical in a reaction independent of superoxide. Since iron salts, ascorbate and activated phagocytes are present in the rheumatoid joint, experiments were designed to see whether ascorbate-dependent or superoxide-dependent formation of hydroxyl radicals would be more important in vivo. 2. in the present study, addition of ascorbate to a superoxide-generating system at concentrations of 100 μmol/l provoked a superoxide-independent formation of hydroxyl radicals for a short period. Lower concentrations of ascorbate did not do this. It is therefore suggested that the superoxide-dependent reaction is probably more important. 3. It is further suggested that destruction of ascorbate by oxygen radicals formed by activated phagocytes accounts for the previously reported low concentrations of this compound in the serum and synovial fluid of rheumatoid patients.

scholarly journals Surface Electrochemistry of Uranium Dioxide in Acidic Hydrogen Peroxide Solutions

2012 ◽  
Vol 1475 ◽  
Author(s):  
Mayuri Razdan ◽  
David Hall ◽  
David W. Shoesmith
Keyword(s):  
Hydrogen Peroxide ◽  
Surface Layer ◽  
Electrochemical Reduction ◽  
Surface Diffusion ◽  
Uranium Dioxide ◽  
Electrode Surface ◽  
Surface Electrochemistry ◽  
Ph Range ◽  
Acidic Hydrogen

ABSTRACTThe electrochemical reduction of H2O2 on SIMFUEL was investigated over the pH range 1 to 4. The mechanism at pH 4 is known to occur on UV species incorporated into a surface layer of UIV1-2xUV2xO2+x. However, below pH 3, reduction occurs on an adsorbed UVO2(OH) state which is unstable and oxidizes to insulating UVI before dissolving as UO22+. Both schemes are observed at intermediate pH’s. The presence of both low and high acidic regions at the electrode surface is determined by the combination of peroxide concentration, bulk pH and the surface diffusion conditions.

scholarly journals Production of the Hydroxyl Radical and Removal of Formaldehyde by Calcined Green Tuff Powder and Tile

2019 ◽  
Vol 11 (12) ◽  
pp. 3390 ◽  
Author(s):  
Toyohisa Fujita ◽  
Lanyin Zhang ◽  
Gjergj Dodbiba ◽  
Ji-Whan Anh ◽  
Yuezhou Wei ◽  
...  
Keyword(s):  
Hydrogen Peroxide ◽  
Hydroxyl Radical ◽  
Hydroxyl Radicals ◽  
Uv Light ◽  
Adsorption Rate ◽  
Optimum Temperature ◽  
High Adsorption ◽  
Alkaline Conditions ◽  
Formaldehyde Adsorption ◽  
High Decomposition Rate

Waste green tuff powder produced by cutting Towada stone has been utilized to eliminate formaldehyde related to greenhouse gases. The green tuff contains TiO2 on zeolite as observed by scanning electron microscope (SEM)t. The green tuff is a natural catalyst that can produce hydrogen peroxide with moisture and oxygen with light. The optimum temperature for calcination of the green tuff powder has been investigated in order to produce hydroxyl radicals from the decomposition of hydrogen peroxide using ultraviolet light (UV) and no light. The green tuff calcined at 800 °C showed a high decomposition rate of hydrogen peroxide with no UV light under high alkaline conditions when measured by using ESR. With UV light, the optimum temperature for calcination of green tuff powder in order to reduce the hydroxyl radical was also 800 °C. Next, the powder calcined at 800 °C was used to produce the tile by compression and heating, and then the formaldehyde adsorption rate was measured. The green tuff powder calcined at 800 °C showed a high adsorption rate, similar to that of the activated carbon. The tiles formed at 40 MPa and heated at 1100 °C were the strongest and also showed adsorption with respect to formaldehyde. The adsorbed formaldehyde on the green tuff tile and powder was possibility decomposed by the hydroxyl radical produced by photocatalysis.

scholarly journals Superoxide dismutase enhances the formation of hydroxyl radicals in the reaction of 3-hydroxyanthranilic acid with molecular oxygen

1988 ◽  
Vol 251 (3) ◽  
pp. 893-899 ◽  
Author(s):  
H Iwahashi ◽  
T Ishii ◽  
R Sugata ◽  
R Kido
Keyword(s):  
Hydrogen Peroxide ◽  
Superoxide Dismutase ◽  
Hydroxyl Radical ◽  
Molecular Oxygen ◽  
Hydroxyl Radicals ◽  
Fenton Reaction ◽  
Potassium Phosphate ◽  
Radical Formation ◽  
Superoxide Anions ◽  
Hydroxyanthranilic Acid

Superoxide dismutase (SOD) enhanced the formation of hydroxyl radicals, which were detected by using the e.s.r. spin-trapping technique, in a reaction mixture containing 3-hydroxyanthranilic acid (or p-aminophenol), Fe3+ ions, EDTA and potassium phosphate buffer, pH 7.4. The hydroxyl-radical formation enhanced by SOD was inhibited by catalase and desferrioxamine, and stimulated by EDTA and diethylenetriaminepenta-acetic acid, suggesting that both hydrogen peroxide and iron ions participate in the reaction. The hydroxyl-radical formation enhanced by SOD may be considered to proceed via the following steps. First, 3-hydroxyanthranilic acid is spontaneously auto-oxidized in a process that requires molecular oxygen and yields superoxide anions and anthranilyl radicals. This reaction seems to be reversible. Secondly, the superoxide anions formed in the first step are dismuted by SOD to generate hydrogen peroxide and molecular oxygen, and hence the equilibrium in the first step is displaced in favour of the formation of superoxide anions. Thirdly, hydroxyl radicals are generated from hydrogen peroxide through the Fenton reaction. In this Fenton reaction Fe2+ ions are available since Fe3+ ions are readily reduced by 3-hydroxyanthranilic acid. The superoxide anions do not seem to participate in the reduction of Fe3+ ions, since superoxide anions are rapidly dismuted by SOD present in the reaction mixture.

scholarly journals Ferrous ion-EDTA-stimulated phospholipid peroxidation. A reaction changing from alkoxyl-radical- to hydroxyl-radical-dependent initiation

1984 ◽  
Vol 224 (3) ◽  
pp. 697-701 ◽  
Author(s):  
J M C Gutteridge
Keyword(s):  
Hydrogen Peroxide ◽  
Lipid Peroxidation ◽  
Hydroxyl Radical ◽  
Hydroxyl Radicals ◽  
Superoxide Radicals ◽  
Ferrous Ion ◽  
Radical Scavengers ◽  
Alkoxyl Radical ◽  
Phospholipid Peroxidation ◽  
Hydroxyl Radical Scavengers

The stimulatory effect of ferrous salts on the peroxidation of phospholipids can be enhanced by EDTA when the concentration of Fe2+ in the reaction is greater than that of EDTA. Hydroxyl-radical scavengers do not inhibit peroxidation until the concentrations of Fe2+ and EDTA in the reaction are equal. Lipid peroxidation is then substantially initiated by hydroxyl radicals derived from a Fenton-type reaction requiring hydrogen peroxide. Superoxide radicals appear to play some role in the formation of initiating species.

scholarly journals Metal Complexes Containing Redox-Active Ligands in Oxidation of Hydrocarbons and Alcohols: A Review

Catalysts ◽  
2019 ◽  
Vol 9 (12) ◽  
pp. 1046 ◽  
Author(s):  
Georgiy B. Shul’pin ◽  
Yuriy N. Kozlov ◽  
Lidia S. Shul’pina
Keyword(s):  
Hydrogen Peroxide ◽  
Hydroxyl Radical ◽  
Hydroxyl Radicals ◽  
Oxidation States ◽  
Acetonitrile Molecule ◽  
Oxidation Of Hydrocarbons ◽  
Alkyl Hydroperoxides ◽  
Redox Active ◽  
Tert Butyl Hydroperoxide ◽  
Saturated And Aromatic Hydrocarbons

Ligands are innocent when they allow oxidation states of the central atoms to be defined. A noninnocent (or redox) ligand is a ligand in a metal complex where the oxidation state is not clear. Dioxygen can be a noninnocent species, since it exists in two oxidation states, i.e., superoxide (O2−) and peroxide (O22−). This review is devoted to oxidations of C–H compounds (saturated and aromatic hydrocarbons) and alcohols with peroxides (hydrogen peroxide, tert-butyl hydroperoxide) catalyzed by complexes of transition and nontransition metals containing innocent and noninnocent ligands. In many cases, the oxidation is induced by hydroxyl radicals. The mechanisms of the formation of hydroxyl radicals from H2O2 under the action of transition (iron, copper, vanadium, rhenium, etc.) and nontransition (aluminum, gallium, bismuth, etc.) metal ions are discussed. It has been demonstrated that the participation of the second hydrogen peroxide molecule leads to the rapture of O–O bond, and, as a result, to the facilitation of hydroxyl radical generation. The oxidation of alkanes induced by hydroxyl radicals leads to the formation of relatively unstable alkyl hydroperoxides. The data on regioselectivity in alkane oxidation allowed us to identify an oxidizing species generated in the decomposition of hydrogen peroxide: (hydroxyl radical or another species). The values of the ratio-of-rate constants of the interaction between an oxidizing species and solvent acetonitrile or alkane gives either the kinetic support for the nature of the oxidizing species or establishes the mechanism of the induction of oxidation catalyzed by a concrete compound. In the case of a bulky catalyst molecule, the ratio of hydroxyl radical attack rates upon the acetonitrile molecule and alkane becomes higher. This can be expanded if we assume that the reactions of hydroxyl radicals occur in a cavity inside a voluminous catalyst molecule, where the ratio of the local concentrations of acetonitrile and alkane is higher than in the whole reaction volume. The works of the authors of this review in this field are described in more detail herein.

Nonylphenols degradation in the UV, UV/H2O2, O3 and UV/O3 processes – comparison of the methods and kinetic study

2015 ◽  
Vol 71 (3) ◽  
pp. 446-453 ◽  
Author(s):  
E. Felis ◽  
K. Miksch
Keyword(s):  
Aqueous Solution ◽  
Hydrogen Peroxide ◽  
Hydroxyl Radicals ◽  
Rate Constants ◽  
Uv Light ◽  
Second Order ◽  
Quantum Yields ◽  
Environmental Significance ◽  
Order Rate ◽  
Technical Mixture

This paper describes the results of experiments on the decomposition of selected nonylphenols (NPs) in aqueous solutions using the UV, UV/H2O2, O3 and UV/O3 processes. The goal of the research was to determine the kinetic parameters of the above-mentioned processes, and to estimate their effectiveness. These substances were selected because of their ubiquitous occurrence in the aquatic environment, resistance to biodegradation and environmental significance. As a result of the experiments, the quantum yields of the 4-n-nonylphenol (4NP) and NP (technical mixture) photodegradation in aqueous solution were calculated to be 0.15 and 0.17, respectively. The values of the second-order rate constants of the investigated compounds with hydroxyl radical and NP with ozone were also determined. The estimated second-order rate constants of 4NP and NP with hydroxyl radicals were equal to 7.6 × 108–1.3 × 109 mol−1 L s−1. For NP, the determined rate constant with ozone was equal to 2.01 × 106 mol−1 L s−1. The performed experiments showed that NP was slightly more susceptible to degradation by the UV radiation and hydroxyl radicals than 4NP. The study demonstrated also that the polychromatic UV-light alone and also in combination with selected oxidizers (i.e. hydrogen peroxide, ozone) may be successfully used for the removal of selected NPs from the aqueous medium.

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