Speciation of iron (II) and (III) by using solvent extraction and flame atomic absorption spectrometry

A method for speciation, preconcentration and separation of Fe²⁺ and Fe³⁺ in different matrices was developed using solvent extraction and flame atomic absorption spectrometry. PAN as complexing reagent for Fe²⁺ and chloroform as organic solvent were used. The complex of Fe²⁺-PAN was extracted into chloroform phase in the pH range of 0.75-4.0 and Fe³⁺ remains in water phase in the pH range 0.75-1.25. The optimum conditions for maximum recovery of Fe²⁺ and minimum recovery of Fe³⁺ were determined as pH = 1, the stirring time of 20 min, the PAN amount of 0.5 mg and chloroform volume of 8 mL. The developed method was applied to the determination of Fe²⁺ and Fe³⁺ in tea infusion, fruit juice, cola and pekmez. It is seen that there is high bioavailable iron (Fe²⁺) in pekmez. The developed method is sensitive, simple and need the shorter time in comparison with other similar studies.     

Separation and indirect ultraviolet detection of ferrous and trivalent iron ions by using ionic liquids in ion chromatography

A method of simultaneous separation and indirect ultraviolet detection of different valence iron ions Fe²⁺ and Fe³⁺ by using ionic liquids as mobile phase additives and ultraviolet absorption reagents on a cation exchange column functionalized with carboxylic acid group was developed. The effects of ionic liquids, organic acids, detection wavelength, etc. on separation and detection of Fe²⁺ and Fe³⁺ were investigated and the mechanism was discussed. The pyridinium and imidazolium ionic liquids were not only ultraviolet absorption reagents of indirect ultraviolet detection but also effective components for separating Fe²⁺ and Fe³⁺. The separation and detection of Fe²⁺ and Fe³⁺ can be achieved using 0.5 mmol/L pyridinium ionic liquid?1.2 mmol/L methanesulfonic acid as the mobile phase. The determination of Fe²⁺ and Fe³⁺ had a good linear relationship in the concentration range of 1?100 mg/L. The limits of detection of Fe²⁺ and Fe³⁺ were 0.12 and 0.09 mg/L, respectively. This method was applied to the actual sample detection in the field of medical analysis. The spiked recoveries were between 97.3 and 99.5%, and the relative standard deviations were less than 0.6%. The method is simple, accurate, and reliable, and is an analytical method with universal and practical value.     

Chromo-chemodosimetric detection for Fe2+ by Fenton reagent-induced chromophore-decolorizing of halogenated phenolsulfonphthalein derivatives

A commercially-available sulfonphthalein derivative was demonstrated to be a chemodosimeter for Fe²⁺ and its sensing behavior was further investigated by UV-vis spectroscopy in aqueous media under the optimum conditions. In the presence of chlorophenol red (CPR) and H₂O₂, the absorption maximum at 435 nm decreased upon addition of Fe²⁺, resulting in a significant color change of the CPR solution from yellow to colorless. The chemosensor system did not show significant responses to a series of other metal ions including Al³⁺, Zn²⁺, Cd²⁺, Hg²⁺, Mn²⁺, Co²⁺, Fe³⁺, Ni²⁺, Cu²⁺, La³⁺, Ce⁴⁺, Th⁴⁺, Pd²⁺, Pb²⁺, Sb³⁺, Cr³⁺, Au³⁺, Ag⁺, Nd³⁺, Sm³⁺, alkali and alkaline earth metal cations, allowing for highly selective naked-eye detection of Fe²⁺. Quantitative analysis was carried out kinetically for practicable the Fe²⁺ assay when either fixed time method or the initial rate method was applied. When the detecting time was set, the decrease of absorbance signal was linear with Fe²⁺ concentration in the range of 0 to 7.50 × 10^?5 mol L^?1 and the regression equation was ΔA = 0.00759 + 0.00593C _Fe with a correlation coefficient r = 0.9953. The chemodosimetric system has employed an irreversible Fenton reagent-promoted oxidation of the CPR free chromophore and the hydroxyl radicals were generated in the presence of both Fe²⁺ and hydrogen peroxide. The mechanistic interpretation of the signaling process was partially confirmed by the radical scavenging experiment and the FT-IR analysis of the intermediates formed at different reaction periods.     

High-energy-density LiMn0.7Fe0.3PO4 nanorods synthesized by microwave-assisted solvothermal method

Microwave-assisted solvothermal method has been developed for synthesizing LiMn_0.7Fe_0.3PO₄ cathode materials with an olivine structure. The obtained LiMn_0.7Fe_0.3PO₄ nanorods were characterized by X-ray diffraction, scanning and transmission electron microscope, Brunauer-Emmett-Teller surface area measurements, and electrochemical tests. Electrochemical tests clearly indicate that the as-made LiMn_0.7Fe_0.3PO₄ nanorods exhibit two redox activities of Fe³⁺/Fe²⁺ and Mn³⁺/Mn²⁺ couple at galvanostatic charge-discharge process, which is due to the coexistence of Mn²⁺ with Fe²⁺ at 4c sites. The as-synthesized materials have high energy density, excellent rate capability and cycling stability.     

On‐surface Fenton and Fenton‐like reactions appraised by paper spray ionization mass spectrometry

On‐surface degradation of sildenafil (an adequate substrate as it contains assorted functional groups in its structure) promoted by the Fenton (Fe²⁺/H₂O₂) and Fenton‐like (Mⁿ⁺/H₂O₂; Mⁿ⁺ = Fe³⁺, Co²⁺, Cu²⁺, Mn²⁺) systems was investigated by using paper spray ionization mass spectrometry (PS‐MS). The performance of each system was compared by measuring the ratio between the relative intensities of the ions of m/z 475 (protonated sildenafil) and m/z 235 (protonated lidocaine, used as a convenient internal standard and added to the paper just before the PS‐MS analyzes). The results indicated the following order in the rates of such reactions: Fe²⁺/H₂O₂ ≫ H₂O₂ ≫ Cu²⁺/H₂O₂ > Mⁿ⁺/H₂O₂ (Mⁿ⁺ = Fe³⁺, Co²⁺, Mn²⁺) ~ Mⁿ⁺ (Mⁿ⁺ = Fe²⁺, Fe³⁺, Co²⁺, Cu²⁺, Mn²). The superior capability of Fe²⁺/H₂O₂ in causing the degradation of sildenafil indicates that Fe²⁺ efficiently decomposes H₂O₂ to yield hydroxyl radicals, quite reactive species that cause the substrate oxidation. The results also indicate that H₂O₂ can spontaneously decompose likely to yield hydroxyl radicals, although in a much smaller extension than the Fenton system. This effect, however, is strongly inhibited by the presence of the other cations, ie, Fe³⁺, Co²⁺, Cu²⁺, and Mn²⁺. A unique oxidation by‐product was detected in the reaction between Fe²⁺/H₂O₂ with sildenafil, and a possible structure for it was proposed based on the MS/MS data. The on‐surface reaction of other substrates (trimethoprim and tamoxifen) with the Fenton system was also investigated. In conclusion, PS‐MS shows to be a convenient platform to promptly monitor on‐surface oxidation reactions.     

Elucidation of methyl tert-butyl ether degradation with Fe/H2O2 by purge-and-trap gas chromatography-mass spectrometry

Degradation of methyl tert-butyl ether (MTBE) with Fe²⁺/H₂O₂ was studied by purge-and-trap gas chromatography-mass spectrometry. MTBE was degraded 99% within 120 min under optimum conditions. MTBE was firstly degraded rapidly based on a Fe²⁺/H₂O₂ reaction and then relatively slower based on a Fe³⁺/H₂O₂ reaction. The dissolved oxygen decreased rapidly in the Fe²⁺/H₂O₂ reaction stage, but showed a slow increase in the Fe³⁺/H₂O₂ reaction stage. tert-Butyl formate, tert-butyl alcohol, methyl acetate and acetone were identified as primary degradation products by mass spectrometry. A preliminary reaction mechanism involving two different pathways for the degradation of MTBE with Fe²⁺/H₂O₂ was proposed. This study suggests that degradation of MTBE can be achieved using the Fe²⁺/H₂O₂ process.     

Selective Chemosensor of Fe3+ Based on Fluorescence Quenching by 2,2′‐Bisbenzimidazole Derivative in Aqueous Media

2,2′‐Bisbenzimidazole derivative ( L ) was designed as a fluorescent chemosensor for Fe³⁺. This structurally simple chemosensor displays significant fluorescence quenching with increasing concentrations of Fe³⁺. L exhibited high selectivity and antidisturbance for Fe³⁺ among environmentally relevant metal ions in aqueous media. The method of Job's plot indicated the formation of 1:2 complex between L and Fe³⁺, and the possible binding mode of the system was also proposed. In addition, further study demonstrates the detection limit on fluorescence response of the sensor to Fe³⁺ is down to 10^?7 mol·L^?1 range. The binding mode was investigated by fluorescence spectra, ESI‐MS, IR data, ¹H NMR, ¹³C NMR and crystal data.     

Chemoselective Thioacetalisation of Aldehydes Catalysed by Fe3+-Montmorillonite #

Aldehydes were cleanly and selectively converted to the corresponding dithioacetals almost quantitatively with catalytic amounts of Fe³⁺-exchanged montmorillonite (Fe³⁺-mont) even in the presence of ketones.

     

Determination of the oxygen balance in oxide superconductors by a photometric method

Summary A photometric method is described for determining the oxygen balance in oxide superconductors. It is based on the oxidation of Fe²⁺ to Fe³⁺ by the superconductors and the following determination of the residual Fe²⁺ ions as complex with 1,10-phenanthroline. Hydrobromic acid is used for dissolving the samples. The method has been developed for 10 mg sample weights. Good reliability of the method was verified by comparison with the cerimetric determination using 80 mg samples.     

The adsorption of dopamine on gold and its interactions with iron(III) ions studied by microcantilevers

The adsorption of dopamine (DA) molecules on gold and their interactions with Fe³⁺ were studied by a microcantilever in a flow cell. The microcantilever bent toward the Au side with the adsorption of DA due to the change of surface stress induced by the intermolecular hydrogen bonds of DA or the charge transfer effect between adsorbates and the substrate. The interaction process between DA adsorbates and Fe³⁺ was revealed by the deflection curves of microcantilever. As indicated by the appearance of a variation during the decline of curves, two steps were observed in the curve at relative high concentrations of Fe³⁺. In this case, Fe³⁺ reacted with DA molecules only in the outer layers and the complexes removed with solution. Then Fe³⁺ reacted further with DA molecules forming the surface complex in the first layer next to the gold. At this stage, the stability of surface complexes was time dependent, i.e., unstable initially and stable finally. This may be due to the surface complexes change from mono-dentate to bi-dentate complexes. In another case, i.e., at relative low concentration of Fe³⁺, only the first step was observed as indicated by the absence of a variation. X-ray photoelectron spectroscopy (XPS) and cycling voltammetry (CV) results provided complementary evidence for the result of microcantilever and proposal. As low as 5 × 10⁻¹⁰ M Fe³⁺ was detected by DA modified microcantilever with a good selectivity over other common metal ions.     

Effect of [Fe2+/total metal] on treatment of heavy metals from laboratory wasteliquid by ferrite process

In this study, the X-ray absorption near-edge structure shows that poisonous Cr⁶⁺ in the laboratory wasteliquid were reduced to Cr³⁺ by adding Fe²⁺ at [Fe²⁺/total metal, mole ratio higher than 4:1. The X-ray diffraction analysis shows that greater the [Fe²⁺/total metal] mole ratios used (such as 6:1, 10:1, 20:1 and 30:1), the more spinel-structured ferrites were formed (0.26, 0.30, 0.48 and 0.59). When [Fe²⁺/total metal] mole ratio was larger than 20:1, the saturation magnetization and coercive field were about 5.21 emu/g and 6.2 kOe, respectively. The ferrite precipitates could be recovered as magnitude materials. However, the TCLP test result was beyond the standard of EPA when the [Fe²⁺/total metal] mole ratio was 30:1. The optimum operation for the laboratory wasteliquid by ferrite process in the [Fe²⁺/total metal] mole ratio was 20:1.     

The origins of the colours of yellow,green and blue sapphires

The absorption spectra of natural yellow sapphires are shown to be due to single Fe³⁺ and Fe³⁺  O²⁻  Fe³⁺ pairs, with the latter dominant. Blue and green sapphires have spectra dominated by Fe³⁺  O²⁻  Ti⁴⁺ and Fe²⁺  O²⁻  Fe³⁺ pairs.     

The formation of V-bearing ferrite by aerial oxidation of an aqueous suspension

Stoichiometric V-bearing ferrites, Fe₂VO₄Fe₃O₄ solid solutions, were formed by the aerial oxidation of aqueous suspensions at V⁴⁺/Fe_total molar ratios of 0.034 and 0.072 in the initial solutions, at pH 11.0 and 65°C. At V⁴⁺/Fe_total ratios of from 0.111 to 0.154 in the initial solution, the V-bearing ferrites formed were slightly further oxidized. At ratios above 0.20 in the initial solution, α-FeOOH was formed together with V-bearing ferrites having a higher V⁴⁺ content, and the ferrites were further oxidized in the course of the aerial oxidation and drying.     

Heterogeneous Fenton Degradation of Organic Pollutants in Water Enhanced by Combining Iron-type Layered Double Hydroxide and Sulfate

Water pollution derived from organic pollutants is one of the global environmental problems. The Fenton reaction using Fe²⁺ as a homogeneous catalyst has been known as one of clean methods for oxidative degradation of organic pollutants. Here, a layered double hydroxide (Fe²⁺Al³⁺-LDH) containing Fe²⁺ and Al³⁺ in the structure was used to develop a “heterogeneous” Fenton catalyst capable of mineralizing organic pollutants. We found that sulfate ion (SO₄²⁻) immobilized on the Fe²⁺Al³⁺-LDH significantly facilitated oxidative degradation (mineralization) of phenol as a model compound of water pollutants to carbon dioxide (CO₂) in a heterogeneous Fenton process. The phenol conversion and mineralization efficiency to CO₂ reached >99% and ca. 50%, respectively, even with a reaction time of only 60 min.     

Separation and Speciation of Iron Ions by Using Colorimetric Hydrogels

In this study, Fe³⁺ ion selective N-(Rhodamine-6G)lactam-N'-acryloyl-ethylenediamine (RH6GAC) monomer was synthesized. Then, p(Acrylamide-co-N-(Rhodamine-6G)lactam-N'-acryloyl-ethylenediamine) (p(AAm-co-RH6GAC)) and p(2-hydroxyethyl- methacrylate-co- N-(Rhodamine-6G)lactam-N'-acryloyl-ethylenediamine) (p(HEMA-co-RH6GAC)) colorimetric hydrogels were synthesized by using acrylamide (AAm) and 2-hydroxyethylmethacrylate (HEMA) as primary monomers. FT-IR, SEM, polymerization yield and swelling characterizations were conducted for the resulting hydrogels. Then, these hydrogels were used in selective absorption of Fe³⁺ ions from aqueous media. The hydrogels, which could absorb Fe³⁺ ions selectively from a mixture of metal ions, were used as column packing material. The solutions containing Fe²⁺ and Fe³⁺ ions at different concentrations were separated at a rate of 97.7 ± 0.7%.     

13C NMR spectra of benzofuroxan and related compounds

The ¹³C n.m.r. spectrum of benzofuroxan at ?15°C is assigned on the basis of selective decoupling experiments and by comparison with the ¹³C chemical shifts of model compounds. The ¹³C spectra were also measured in trifluoroacetic acid as a solvent. From the temperature dependence of the ¹³C spectrum of benzofuroxan in CDCl₃, a barrier of 14·0 ± 0·2 kcal mol^?1 is obtained for the degenerate tautomerism in this compound.     

Preparation of Silver Nanoparticles Reduced by Formamidinesulfinic Acid and Its Application in Colorimetric Sensor

A rapid one-step preparation approach of silver nanoparticles (AgNPs) was reported by employing formamidinesulfinic acid as reducing agent and soluble starch as stabilizing agent. The formation of AgNPs was further confirmed by using UV–Vis absorption spectroscopy, X-ray diffraction spectroscopy and transmission electron microscopy techniques. The resultant AgNPs could be directly used for the colorimetric reaction with metal ions. The results showed that Al³⁺, Cr³⁺, Fe³⁺ and Hg²⁺ ions could induce the color change of AgNPs from yellow to pink (Al³⁺), orange (Cr³⁺) and colorless (Fe³⁺ and Hg²⁺), respectively, which can be observed by the naked eye. Based on these, a sensitive colorimetric sensor for Al³⁺, Fe³⁺, Cr³⁺ and Hg²⁺ ions detection was developed.     

Analysis on the removal of ammonia nitrogen using peroxymonosulfate activated by nanoparticulate zero-valent iron

Nanoparticulate zero-valent iron (Fe⁰) was used to activate peroxymonosulfate (PMS) to remove low concentration of ammonia nitrogen in the aqueous system. The removal process was investigated under various conditions. It was indicated that the removal of \({\text{NH}}_{4}^{ + }\) followed the pseudo-first-order kinetic model for the initial reactions. The removal rate increased with the ascending of pH and Fe⁰ dosage, while declined with the ascent of initial \({\text{NH}}_{4}^{ + }\) concentration. The existence of nitrogenous compounds would inhibit the reactions, especially for the compounds with carboxyl structure functional groups. The identification of free radical proved that \(\cdot {\text{SO}}_{4}^{ - }\) is the main radical in Fe⁰/PMS for the removal of ammonia nitrogen. The inorganic products including \({\text{NO}}_{2}^{ - }\), \({\text{NO}}_{3}^{ - }\), Fe²⁺ and Fe³⁺ were detected with the detailed mechanism proposed. The results demonstrated that Fe⁰/PMS process was more effective on ammonia removal compared to single Fe⁰, Fe⁰/persulfate and Fe⁰/H₂O₂. This study proposed a cost-effective process for \({\text{NH}}_{4}^{ + }\) removal at very low concentration of sulfate radicals.     

A pyrene-based dual chemosensor for colorimetric detection of Cu2+ and fluorescent detection of Fe3+

A pyrene based chemosensor was designed and synthesized. The pyrene fluorophore was connected with a pyridine unit through a Schiff base structure to give the sensor (L). L was tested with a variety of metal ions and exhibited high colorimetric selectivities for Cu²⁺ and Fe³⁺ over other ions. Upon binding with Cu²⁺ or Fe³⁺, L showed an obvious optical color change from colorless to pink for Cu²⁺ or orange for Fe³⁺ over a wide pH range from 3 to 12. Moreover, the fluorescence of L at 370 nm decreased sharply after bonding with Fe³⁺, while other metal ions including Cu²⁺ had no apparent interference. Thus, using such single chemosensor, Cu²⁺ and Fe³⁺ can be detected independently with high selectivity and sensitivity. The limits of detection toward Cu²⁺ and Fe³⁺ were 8.5 and 2.0 μM, respectively. DFT calculation results also proved the formation of stable coordination complexes and the phenomenon of fluorescence quenching by Fe³⁺. Furthermore, L was also successfully used as a bioimaging reagent for detection of Fe³⁺ in living cells.     

Photo‐Assisted Immobilized Fenton Degradation up to pH 8 of Azo Dye Orange II Mediated by Fe3+/Nafion/Glass Fibers

Fe³⁺ Ions have been immobilized into very thin Nafion films cast onto a glass‐fiber mat immersed in an alcoholic solution of Nafion oligomers. This immobilized Fenton catalyst was used to abate/mineralize the azo dye Orange II, taken as a model organic compound. The abatement of Orange II on the Fe³⁺/Nafion/glass fibers was observed to proceed within the same time period as when Nafion alone was used to immobilize the Fe³⁺ ions during the photo‐Fenton reaction. The amount of Nafion in the Nafion Fe³⁺/Nafion/glass fibers was ca. 15 times less per unit surface area compared to Fe³⁺‐exchanged on conventional Nafion membranes used to immobilize Fe³⁺ ions. Orange II solutions under visible‐light irradiation in the presence of H₂O₂ were mineralized up to pH 8 with a kinetics comparable to that found during the degradation runs at pH 3. Repetitive mineralization cycles mediated by the Fe³⁺/Nafion/glass fibers under visible light did not show any decrease in the activity of the immobilized catalysts. A reaction mechanism consistent with the experimental data is suggested. The morphology of the Fe³⁺/Nafion/glass fibers was characterized by scanning electron microscopy (SEM) showing thin Nafion films cast deposited on the glass fibers. Transmission‐electron‐microscopy (TEM) micrographs reveal Fe³⁺‐oxy‐hydroxide particles of 3 – 6 nm before and after repetitive Orange II photodegradation. X‐Ray photoelectron spectroscopy (XPS) provided the evidence for the existence of Fe clusters on the topmost layer of the catalyst mainly as Fe^III. The improvements brought by the glass fibers are a) the use of low quantities of expensive Nafion supported on glass mats to achieve dye degradation rates comparable to Nafion alone and b) Fenton‐mediated degradation of azo dyes at pH 8 without the costly initial acidification usually needed for this type of treatment.