Photocatalytic reaction by Fe(III)–citrate complex and its effect on the photodegradation of atrazine in aqueous solution

The photodegradation of atrazine in aqueous solutions containing citrate and Fe(III) was studied under Xe lamp irradiation on a time scale of hours. It was found that the presence of Fe(III)–citrate complex enhanced the photodegradation rate of atrazine as a result of OH attack. Atrazine photodegradation followed first-order reaction kinetics and the rate depended upon pH and light intensity. High citrate concentrations led to increased photodegradation of atrazine due to the fact that citrate not only acted as a carboxylate ligand but also a reductant of Fe(III). The interaction of Fe(III) with citrate was characterized using UV–visible absorption and Fourier-transform infrared (FTIR) spectroscopy, indicating that the hydrogen ions on the carboxyl groups were exchanged for Fe(III) ions. On the basis of these results, a reaction scheme was proposed in which the cycling of iron and carbon, the depletion of citrate and O₂, and the formation of reactive oxygen species (ROS) were involved.     

Fe(III)-pyruvate and Fe(III)-citrate induced photodegradation of glyphosate in aqueous solutions

The photolysis of Fe(III)-pyruvate and Fe(III)-citrate complexes in water produces hydroxyl radicals in the presence of dissolved oxygen, and can promote the oxidation of organic compounds. The photodegradation of glyphosate with Fe(III)-pyruvate and Fe(III)-citrate complexes was investigated under irradiation at λ?≥?365?nm. The effect of initial concentration of glyphosate, the initial pH value, and the Fe(III)/carboxylate ratio were examined. Upon irradiation of glyphosate aqueous solution with the complexes in the acidic range of natural waters, the bioavailable orthophosphate could be released from degradation of glyphosate. The amount of orthophosphate increased with increasing Fe(III)/carboxylate ratio.     

Simultaneous determination of Fe(II) and Fe(III) by kinetic spectrophotometric H-point standard addition method

The H-point standard addition method (HPSAM) for simultaneous determination of Fe(II) and Fe(III) is described. The method is based on the difference in the rate of complex formation of iron in two different oxidation states with Gallic acid (GA) at pH 5. Fe(II) and Fe(III) can be determined in the range of 0.02–4.50 μg ml⁻¹ and 0.05–5.00 μg ml⁻¹, respectively, with satisfactory accuracy and precision in the presence of other metal ions, which rapidly form complexes with GA under working conditions. The proposed method was successfully applied for simultaneous determination of Fe(II) and Fe(III) in several environmental and synthetic samples with different concentration ratios of Fe(II) and Fe(III).     

Influence of the chain and layer structure of Fe(III) and In(III) aqua-pentachloro-complexes on the bending vibrations of water molecules

Studies of IR and Raman spectra of monohydrates M^I₂[M^IIICl₅(H₂O)] (where M^I=K⁺, Rb⁺, Cs⁺ and M^III=Fe³⁺, In³⁺) at 1400-1900 cm⁻¹ have been carried out. The medium intensity band, detected in the region 1580-1595 cm⁻¹ was assigned to bending vibrations of water molecules (δHOH). The shift of the δHOH band towards low wavenumbers (1580-1595 cm⁻¹) is a main sign of the water molecule interactions in the chain hydrates. Additionally in the IR and Raman spectra of these salts, the appearance of the low intensity band between 1750 and 1810 cm⁻¹ (ν_x(H₂O)) was observed. In the presented paper we also discuss the influence of M^I and M^III cations on the position and splitting of these bands.     

Simple flow injection method for simultaneous spectrophotometric determination of Fe(II) and Fe(III)

The method is based on spectrophotometric determination of Fe(II) and Fe(III) at a single wavelength (530 nm) with the use of a dedicated reversed-flow injection system. In the system, EDTA solution is injected into a carrier stream (HNO₃) and then merged with a sample stream containing a mixture of sulfosalicylic acid and 1,10-phenanthroline as indicators. In an acid environment (pH ≅ 3) the indicators form complexes with both Fe(III) and Fe(II), but EDTA replaces sulfosalicylic acid, forming a more stable colourless complex with Fe(III), whereas Fe(II) remains in a complex with 1,10-phenenthroline. As a result, the area and minimum of the characteristic peak can be exploited as measures corresponding to the Fe(III) and Fe(II) concentrations, respectively. The analytes were not found to affect each other's signals, hence two analytical curves were constructed with the use of a set of standard solutions, each containing Fe(II) and Fe(III). Both analytes were determined in synthetic samples within the concentration ranges of 0.05–4.0 and 0.09–6.0 mg L⁻¹, respectively, with precision less than 1.5 and 2.6% (RSD) and with accuracy less than 4.3 and 5.6% (RE). The method was applied to determination of the analytes in water samples collected from artesian wells and the results of the determination were consistent with those obtained using the ICP-OES technique.     

Photochemical degradation of environmentally persistent perfluorooctanoic acid (PFOA) in the presence of Fe(III)

Environmentally persistent and bioaccumulative perfluorooctanic acid (PFOA) was difficult to be decomposed under the irradiation of 254 nm UV light. However, in the presence of 80μmol /L Fe(III), 80% of PFOA with initial concentration of 48μmol/L (20 mg/L) was effectively degraded and 47.8% of fluorine atoms in PFOA molecule were transformed into inorganic fluoride ion after 4 h reaction. Shorter chain perfluorocarboxylic acids bearing C3-C7 and fluoride ion were detected and identified by LC/MS and IC as the degradation products in the aqueous solution. It was proposed that complexes of PFOA with Fe(III) initiated degradation of PFOA irradiated with 254 nm UV light.     

A new efficient adsorbent in the preconcentration studies of the Cr(III) and Fe(III) ions

In this study, the imine‐graphene hybrid material (HM) was used as an adsorbent for removal of Fe(III) and Cr(III) metal ions from the drinking waters. The adsorbent material (HM) was prepared at three steps. At the first step, the graphite was oxidized by Hummer's method for preparation of graphene oxide (GO), in the second step, the silanization derivative (GO‐APTES) was obtained from the reaction of the 3‐(trimethoxysilyl) propylamine and GO. In the final step, the hybrid material (HM) was synthesized from the reaction of the 3,5‐diiodosalicylaldehyde and GO‐APTES. The chemical structures of three materials GO, GO‐APTES and HB were characterized by using the FT‐IR, XRD, EDX, SEM, TEM and UV‐vis methods. Thermal properties of the materials GO, GO‐APTES and HB were investigated by TGA/DTA methods in the 25–1000°C temperature range. Adsorption and desorption studies of the hybrid material toward Fe(III) and Cr(III) metal ions were investigated using the Batch method. The effect of pH, contact time, temperature, concentration on the adsorption properties of the hybrid material were investigated by ICP‐OES. The Fe(III) and Cr(III) ions have the maximum adsorption at the pH 7. The adsorption capacity decreases with the increase in pH values because above pH 9 the adsorption decreases due to the precipitation of metal hydroxide.     

New method for simultaneous determination of Fe(II) and Fe(III) in water using flow injection technique

The method exploits the possibilities of flow injection gradient titration in a system of reversed flow with spectrophotometric detection. In the developed approach a small amount of titrant (EDTA) is injected into a stream of sample containing a mixture of indicators (sulfosalicylic acid and 1,10-phenanthroline). In acid environment sulfosalicylic acid forms a complex with Fe(III), whereas 1,10-phenanthroline forms a complex with Fe(II). Measurements are performed at wavelength λ = 530 nm when radiation is absorbed by both complexes. After injection EDTA replaces sulfosalicylic acid and forms with Fe(III) more stable colourless complex. As a result, a characteristic “cut off” peak is registered with a width corresponding to the Fe(III) concentration and with a height corresponding to the Fe(II) concentration. Calibration was performed by titration of four two-component standard solutions of the Fe(II)/Fe(III) concentrations established in accordance with 2² factorial plan. The method was tested with the use of synthetic samples and then it was applied to the analysis of water samples taken from artesian wells. Under optimized experimental conditions Fe(II) and Fe(III) were determined with precision less than 0.8 and 2.5% (RSD) and accuracy less than 3.2 and 5.1% (relative error) within the concentration ranges of 0.1-3.0 and 0.9-3.5 mg L⁻¹ of both analytes, respectively.     

Fe(III) sequestering agents built on poly(ethylenimine) through crosslinkage of three molecules of a salicylate derivative preassembled by Fe(III) ion

Three molecules of 5-(bromoacetyl) salicylate ( 1 ) complexed to Fe(III) ion were crosslinked with poly(ethylenimine) (PEI) in DMSO by alkylation of amino groups of PEI with 1 , leading to the formation of Fe(Sal)₃PEI, a water-soluble polymer. Several other derivatives including the immobilized form were also prepared. Examination of the values of log K_f for the PEI derivatives indicated that each Fe(III) binding site in Fe(Sal)₃PEI contains three salicylate moieties. In addition, the log K_f revealed that the effective molarity (EM) of the salicylate groups contained in the Fe(III) binding site is ca. 1000M. The high EM value shows that the geometry of the coordination sphere is well conserved during the crosslinkage with PEI of 1 preassembled around Fe(III) ion. In view of the EM value and the pK_a values of salicylic phenols in apo(Sal)₃-PEI, the metal-free form, the three salicylate groups of each Fe(III) binding site appear to occupy proximal positions leading to effective cooperation in Fe(III) binding. Fast, strong, and selective binding of Fe(III) ion by the binding site comprising three salicylate moieties was demonstrated. In addition, rapid demetalation of the resulting complexes as well as chemical stability of the immobilized chelating agents built on PEI were achieved. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1197–1210, 1997     

On-line solid-phase extraction and multisyringe flow injection analysis of Al(III) and Fe(III) in drinking water

A new analytical method was developed for on-line monitoring of residual coagulants (aluminium and iron salts) in potable water. The determination was based on a sequential procedure coupling an extraction/enrichment step of the analytes onto a modified resin and a spectrophotometric measurement of a surfactant-sensitized binary complex formed between eluted analytes and Chrome Azurol S. The optimization of the solid phase extraction was performed using factorial design and a Doehlert matrix considering six variables: sample percolation rate, sample metal concentration, flow-through sample volume (all three directly linked to the extraction step), elution flow rate, concentration and volume of eluent (all three directly linked to the elution step). A specific reagent was elaborated for sensitive and specific spectrophotometric determination of Al(III) and Fe(III), by optimizing surfactant and ligand concentrations and buffer composition. The whole procedure was automated by a multisyringe flow injection analysis (MSFIA) system. Detection limits of 4.9 and 5.6 μg L⁻¹ were obtained for Al(III) and Fe(III) determination , respectively, and the linear calibration graph up to 300 μg L⁻¹ (both for Al(III) and Fe(III)) was well adapted to the monitoring of drinking water quality. The system was successfully applied to the on-site determination of Al(III) and Fe(III) at the outlet of two water treatment units during two periods of the year (winter and summer conditions).     

The excited states of bipyridyl and phenanthroline complexes of Fe(III), Ru(II) and Ru(III): A molecular orbital study

The semiempirical zero-differential-overlap molecular orbital model which was shown in earlier papers in this series to give a good account of the charge transfer and -* spectra of Fe(II) complexes with conjugated ligands such as 2,2-bipyridyl and 1,10-phenanthroline is extended to complexes having openshell ground states, such as those of Fe(III), and to complexes of Ru(II) and Ru(III). The results are used to assign the observed charge transfer and intra-ligand absorption bands to specific orbital transitions. Observed and calculated intensities are in good agreement: reasons are advanced for the much lower intensity of the charge transfer bands in Ru(III) compared to Ru(II) complexes.     

Photocatalytic degradation of chloroform by bis (bipyridine)dichlororuthenium(III/II)

Broadband (λ > 320 nm) irradiation of chloroform solutions of either [Ru(bpy)₂Cl₂] or [Ru(bpy)₂Cl₂]Cl exposed to air led to a photostationary state, in which [Ru(bpy)₂Cl₂]⁺ predominated, and to the continuous decomposition of CHCl₃, as evidenced by the accumulation of HCl, hydroperoxides (CCl₃OOH and CHCl₂OOH), and tetra-, penta-, and hexachloroethane. The addition of Cl^? increased the rate of photodecomposition, while the replacement of Cl^? by F^? greatly decreased the rate. The observations are consistent with a photocatalytic cycle in which [Ru(bpy)₂Cl₂]⁺ is photochemically reduced to [Ru(bpy)₂Cl₂], which is thermally reoxidized by CCl₃OO or CCl₃OOH. In the absence of air a much slower photodecomposition reaction takes place leading to continuously increasing concentrations of chloroethanes. The data are consistent with a catalytic cycle in which [Ru(bpy)₂Cl₂]⁺ is photoreduced, as in aerated solutions, while [Ru(bpy)₂Cl₂] is photooxidized with chloroform as the substrate.     

Synthesis, structures and properties of hydrolytic Al(III) aggregates and Fe(III) analogues formed with iminodiacetate-based chelating ligands

Both Al(III) and Fe(III) display a rich hydrolytic chemistry which can lead to the formation of a variety of aggregated oxo and hydroxo-bridged aggregates. The formation, structures and properties of these species are important in defining the availability and reactivity of these species in aqueous environments such as are found in biological systems and the environment. Although there are many similarities in the behaviour of the Al³⁺ and Fe³⁺ ions there are also some important differences between these two metal ions which can lead to a divergence in their chemistries. These considerations are discussed and illustrated with reference to 16 Al(III) and Fe(III) compounds, which have been crystallographically characterised, and which form in aqueous environments in the presence of chelating ligands containing the iminodiacetate functionality.     

Degradation of carbofuran in aqueous solution by Fe(III) aquacomplexes as effective photocatalysts

The photodegradation of carbofuran by excitation of iron(III) aquacomplexes was investigated under UV irradiation. The degradation rate was strongly influenced by the pH, and initial concentration of Fe(III). The degradation efficiency of carbofuran at the difference pH was in good agreement with the initial concentration of Fe(OH)²⁺ in the solution. An initial carbofuran concentration of 10 mg L⁻¹ was completely degraded within 50 min at pH 2.8 with original Fe(III) concentration of 8 × 10⁻⁴ mol L⁻¹. This degradation reaction was found to follow the first order kinetics law and the rate constant of 1.60 × 10⁻³ s⁻¹ was observed. The decrease of TOC content was observed during the photocatalytic process and the removal percentage obtained was about 70% after 25 h. Furthermore, ammonium ion as an end-product was detected in the solution. Therefore, this process based on the catalytic reaction of Fe(II, III) is responsible for the continuous production of hydroxyl radicals in such system. A gas chromatography-mass spectrometry analysis showed the formation of four photoproducts, such as 2,2-dimethyl-2,3-dihydro-benzofuran-7-ol, etc., revealing that the carbamate branch, C-3 and C-2 positions in furan ring were attack targets of hydroxyl radicals. Based on these results, the photocatalytic system could be useful technology for the treatment and the mineralization of compounds like carbofuran.     

Limitation of ferrozine method for Fe(II) detection: reduction kinetics of micromolar concentration of Fe(III) by ferrozine in the dark

The dark reduction kinetics of micromolar concentrations of Fe(III) in aqueous solution were studied in the presence of millimolar concentrations of ferrozine (FZ) over the pH range 4.0–7.0. A pseudo-first-order kinetics model was used to describe Fe(III) reduction at pH 4.0 and 5.0, and the reduction rate decreased with increasing pH or initial Fe(III) concentration. A more molecular-based kinetics model was developed to describe Fe(III) reduction at pH 6.0 and 7.0. From this model, the intrinsic rate constants (k₁) of Fe(III) reduction by FZ in the dark were obtained as 0.133 ± 0.004 M^?1 s^?1 at pH 6.0 and 0.101 ± 0.009 M^?1 s^?1 at pH 7.0. It was also found in this model that a higher pH, a higher concentration of Fe(III), a lower concentration of FZ and less incubation time led to a lower fraction of Fe(III) reduction by FZ in the dark.     

Studies of the catalytic activity of Fe(III)(salen) complexes as epoxidation catalysts

Two new Fe(III)(salen) complexes, FeL¹ClO₄·2H₂O (1) and FeL²ClO₄ (2) [L¹ = N,N′-ethylenebis(3-formyl-5-methylsalicylaldimine) and L² = N,N′-cyclohexenebis(3-formyl-5-methylsalicylaldimine)], have been synthesized and characterized. The catalytic activity of the complexes for epoxidation of alkenes has been investigated in the presence of two terminal oxidants PhIO and NaOCl, with two solvents CH₃CN and CH₂Cl₂. As alkenes styrene and (E)-stilbene have been chosen for investigation; styrene is a better substrate than electron-rich (E)-stilbene. The study also suggests that unlike their Mn(III) counterparts, 1 and 2 are poor epoxidation catalysts; catalysis proceeds with formation of one intermediate, rather than forming more than one intermediate depending on the terminal oxidant used. Use of exogenous neutral donor ligands such as Py, PyNO and 1-MePy is effective to improve catalytic behavior.     

Phosphoprotein electrophoresis in the presence of Fe(III) ions

Preparation of affinity polyacrylamide gels containing immobilized Fe(III) ions for the separation of proteins exhibiting metal ion binding properties is described. The presented method enables uniform distribution of immobilized metal ions in the affinity part of the polyacrylamide separating gel. Affinity gels prepared by this way are suitable to follow the effect of different concentrations of metal ions immobilized in polyacrylamide gel on a protein electrophoretic behavior. Polyacrylamide gels containing immobilized Fe(III) ions were used to study the electrophoretic behavior of two model proteins differing in their phosphate group content: chicken ovalbumin and bovine α‐casein. For the electrophoretic separation, both the native and the denaturating conditions were used.     

Spectrophotometric Determination of Piroxicam via Chelation with Fe(III) in Commercial Dosage Forms

The objective of this work is to develop and validate spectrophotometric method for the determination of piroxicam in commercial dosage forms. The method is based on the chelation of the drug with Fe(III) to form pink coloured metal chelate at room temperature which absorbs maximally at 504 nm. Beer's law is obeyed over the concentration range of 8–160 μg mL^?1 (A = 1.07 × 10^?3 + 7.75 × 10^?3 C). Under the optimized experimental conditions, proposed method is validated as per the International Conference on Harmonisation guidelines. The limits of detection and quantitation for the proposed method are 0.775 and 2.348 μg mL^?1, respectively. The proposed method has been successfully applied to the determination of piroxicam in commercial dosage forms. The results are compared with the reference El‐Ries et al. spectrophotometric method.     

Enhanced Degradation of Paracetamol by the Fe(III)-Sulfite System under UVA Irradiation

The Fe(III)-S(IV) system used for advanced oxidation processes (AOPs) at acidic pH has just been proposed and demonstrated valid for very few contaminants in the last several years. In this work, we investigated the effect of ultraviolet A (UVA) radiation on the degradation efficiency of the Fe(III)/S(IV) system at near-neutral pH. Paracetamol (PARA) was selected as a model contaminant. The influencing factors, such as initial pH and Fe(III)/S(IV) molar ratio on chemical kinetics, and the mechanism of PARA degradation are investigated, with an emphasis on the determination of dominant oxidant species. Our results show that irradiation enhances the PARA degradation by accelerating the decrease of pH to acidic levels, and the optimal pH for the degradation of PARA in the Fe(III)/S(IV)/O₂ system was around 4.0. At near-neutral pH, more than 60% of PARA was decomposed within 40 min under irradiation, whereas no significant degradation of PARA was observed using Fe(III)/S(IV) at pH 7.0 without irradiation. Mechanism investigation revealed that sulfate radical (SO₄^•‒) is the main oxidant species generated and responsible for the PARA degradation under these conditions. This finding may have promising implications in developing a new degradation process for dealing with wastewater at near-neutral pH by the Fe(III)/S(IV)/O₂ system under UVA irradiation.     

Ru(III), Cr(III), Fe(III) complexes of Schiff base ligands bearing phenoxy Groups: Application as catalysts in the synthesis of vitamin K3

Two polydentade Schiff base ligands and their Ru(III), Cr(III) and Fe(III) complexes were synthesized and characterized by elemental analysis (C, H, N), UV/Vis, FT IR, ¹H and ¹³C NMR, LC–MS/MS, molar conductivity and magnetic susceptibility techniques. The absorption bands in the electronic spectra and magnetic moment measurements verified an octahedral environment around the metal ions in the complexes. The thermal stabilities were investigated using TGA. The synthesized complexes were used in the catalytic oxidation of 2-methyl naphthalene (2MN) to 2-methyl-1,4-naphthoquinone; vitamin K₃, menadione, 2MNQ; using hydrogen peroxide, acetic acid and sulfuric acid. L₁-Fe(III) complex showed very efficient catalytic activity with 58.54% selectivity in the conversions of 79.11%.