Structural Fe(III) reduction in smectites

Manipulation of the oxidation state of structural Fe in clay minerals is a potential method for altering important physical–chemical properties of the clay and several studies have focussed on this phenomenon. This paper summarizes current knowledge on reduction of structural Fe(III) in iron-rich dioctahedral smectites and partial stabilization of Fe(II) in reduced SWa-1 ferruginous smectite via fixation of Li⁺ cations upon heating. Fe(III) in Fe-rich dioctahedral smectites was completely reduced in citrate–bicarbonate buffer using sodium dithionite. Progress in the reduction or reoxidation process was followed by monitoring the Fe(II)–O–Fe(III) intervalence electron transfer transition using visible spectroscopy at 730 nm. Reduction proceeds from basal surfaces rather than from particle edges. One study found that trioctahedral domains and vacancies may occur within the structure of reduced minerals, but another study indicated less radical structural changes. Fully reoxidized minerals contain less OH groups. About 20% of total Fe can be stabilized as Fe(II) in reduced SWa-1 via Li⁺-saturation and heating the Li-form of a highly reduced mineral in N₂ atmosphere at 260 °C for 24 h. Part of the Li⁺ is trapped in previously vacant octahedral sites, forming trioctahedral AlFe(II)LiOH or Fe(III)Fe(II)LiOH groupings.     

Electrochemical oxidation of aliphatic hydrocarbons promoted by inorganic radicals. I. OH radicals

The OH initiated oxidation of aliphatic hydrocarbons by the simultaneous electrochemical reduction of O₂ and of Fe(III) at controlled potential was investigated in the liquid phase over a Fe(III) concentration range 0.5–5 mM. OH radicals were generated by the reaction: Fe(II)+H₂O₂Fe(III)+^.OH+OH^– The compounds studied were the linear alkane hydrocarbons from C₅ to C₁₀ and 3-methyl pentane. The results showed that the ketones are the only reaction products and that the yields decrease with increasing number of carbonium atoms of the hydrocarbon. Decreasing yields were also observed with increasing Fe(III) concentration.     

Photo-enhancement of Cr(VI) reduction by fungal biomass of Neurospora crassa

Various organisms such as fungus are capable of reducing Cr(VI) to less toxic Cr(III). However, light-induced Cr(VI) reduction by fungus is less reported and needs to be explored since anthropogenic or natural activities may bring these two reactants into a sunlit environment. In this study, the interactions and reaction mechanisms of Cr(VI) on a model fungus, Neurospora crassa, were evaluated in the presence or absence of light. The influence of ferric ion, a widely distributed metal, on Cr(VI) reduction by the fungus was also investigated under illumination. The results show that 20–54% of added Cr(VI) (96.2 μM) was removed by 1 g of dead fungal biomass (i.e., 1–2.7 mg Cr(VI) reduction by 1 g biomass) at pH 1–3, after 6 h reaction in the dark. However, 96.2 μM Cr(VI) disappeared completely (i.e., 5 mg Cr(VI) reduction by 1 g biomass) under the same reaction time and experimental conditions when light was present. The rapid disappearance of Cr(VI) in solution was due to the reduction of Cr(VI) by the excited biomass upon light absorption, and the rates of redox reactions increased with a decrease at pH. Cr(VI) reduction could be further increased with the addition of 89.5 μM Fe(III) because the formation of Fe(II) from the photolysis of Fe–organic complexes enhanced Cr(VI) reduction. Spectroscopic studies indicated that the amide, NH, and carboxyl groups of N. c.-biomass may be responsible for initiating Cr(VI) reduction; comparatively, the cyclo-carbons of chitin, glucan, and their derivatives were more persistent to the oxidation by Cr(VI). Accordingly, fungi containing high amount of carboxyl, amide, and NH groups may be preferable as efficient reductants for scavenging Cr(VI) from environment. Upon the absorption of a renewable light source, Cr(VI) could be converted rapidly by the biomaterials to the less toxic Cr(III).     

Electrochemical regeneration of chrome etching solution

A metal surface is chromatized with a chromic acid solution to obtain a good adherence of polymer coatings. In this process Cr(VI) is reduced to Cr(III). The oxidation strength of the solution decreases during use. The chrome solution needs to be regenerated and purified. A new anode material, namely boron-doped diamond, was used to investigate the oxidation of Cr(III) to Cr(VI). It was found that the current efficiency for Cr(III) oxidation decreases with increasing total current density. The current density of Cr(III) oxidation increases linearly with increasing Cr(III) concentration and is practically independent of the Cr(VI) concentration. It was concluded that the diffusion of Cr(III) is the rate-determining step for the Cr(III) oxidation at Cr(III) concentrations form 40 to 160 mol m^–3. The surface of the boron-doped diamond shows no signs of chemical corrosion or mechanical destruction. A filter-press type cell divided into two compartments by a cation exchange membrane was proposed. A cost calculation was carried out for the oxidation of 1.28 mmol s^–1 Cr(III) in a 40 mol m^–3 chrome(III) solution. Factors affecting the feasibility of this process include the costs of chemical waste disposal, the costs of chromic acid, government legislation and to a great extent the costs of the new anode material.     

Spectroscopic and Thermal Studies of Mn(II), Fe(III), Cr(III) and Zn(II) Complexes Derived from the Ligand Resulted by the Reaction Between 4-Acetyl Pyridine and Thiosemicarbazide

Transition metal complexes of Mn(II), Fe(III), Cr(III) and Zn(II) metal ions with a general formulas [Mn(L)₂(Cl)₂]·4H₂O (I), [Fe(L)₂(Cl)₂]·Cl·6H₂O (II), [Cr(L)₂(Cl)₂]·Cl·6H₂O (III) and [Zn(L)₂(Cl)₂]·2H₂O (IV) where L = 4-acetylpyridine thiosemicarbazone, have been synthesized and interpreted using CHN elemental analysis, magnetic susceptibility measurements, molar conductance, thermal analysis and spectroscopic techniques; i.e., infrared, electronic UV/vis, ¹H-NMR and mass. The manganese(II), ferric(III), chromium(III) and zinc(II) complexes have octahedral geometry. The molar conductance measurements reveal that the Mn(II) and Zn(II) chelates are non-electrolytes but Fe(III) and Cr(III) have an electrolytic behavior. The IR spectra show that the 4-acetylpyridine thiosemicarbazone free ligand is coordinated to the metal(II) chlorides as a neutral bidentate ligand through both of the lone pair of electrons of the C=N azomethine group and C=S group. X-ray powder diffraction gives an impression that the resulting complexes are amorphous and different from the start materials. The thermogravimetric studies indicate that uncoordinated water molecules are lost in the first and second decomposition steps. The activation thermodynamic parameters E*, ΔH*, ΔS* and ΔG* are estimated from the differential thermogravimetric analysis (DTG) curves using Horowitz–Metzger (HM) and Coats–Redfern (CR) methods. The ligand and its complexes have been screened for antibacterial and antifungal activities against two bacteria; i.e., Escherichia coli (Gram −ve) and Bacillus subtilis (Gram +ve) and two fungi, i.e., tricoderma and penicillium activities).     

Formation of an unusual copper(II) complex from the degradation of a novel tricopper(II) carbohydrazone complex

An unusual copper(II) complex [Cu(L^1a)₂Cl₂] CH₃OH·H₂O·H₃O⁺Cl⁻ (1a) was isolated from a solution of a novel tricopper(II) complex [Cu₃(HL¹)Cl₂]Cl₃·2H₂O (1) in methanol, where L^1a is 3-(2-pyridyl)triazolo[1,5-a]-pyridine, and characterized with single crystal X-ray diffraction study. The tricopper(II) complex of potential ligand 1,5-bis(di-2-pyridyl ketone) carbohydrazone (H₂L¹) was synthesized and physico-chemically characterized, while the formation of the complex 1a was followed by time-dependant monitoring of the UV–visible spectra, which reveals degradation of ligand backbone as intensity loss of bands corresponding to O → Cu(II) charge transfer.     

Adsorption Characteristics of Chromium(VI) Ions onto Fe(III)-Coordinated Amino-Functionalized Poly(glycidylmethacrylate)-Grafted TiO2-Densified Cellulose

An investigation was conducted with a newly developed adsorbent, iron(III)- coordinated amino-functionalized poly(glycidylmethacrylate)-grafted TiO₂-densified cellulose (Fe(III)-AM-PGDC) on the removal of chromium(VI) from aqueous solution. Batch experiments were performed under various conditions of time, pH, concentration, dose, ionic strength, and temperature. Adsorption of Cr(VI) on Fe(III)-AM-PGDC was dominated by ion exchange or outer-sphere complexation. The maximum adsorption capacity was found to be 109.76 mg g^?1. Thermodynamic study showed that adsorption of Cr(VI) onto Fe(III)-AM-PGDC is more favored. The complete removal of Cr(VI) from electroplating wastewater was achieved by the adsorbent. The adsorbent did not lose its adsorption capacity even after the fourth regeneration.     

Effects of Water and Ion-Exchanged Counterion on the FTIR Spectra of ZSM-5. II. (Cu+–CO)-ZSM-5: Coordination of Cu+–CO Complex by H2O and Changes in Skeletal T–O–T Vibrations

The 2157 cm^–1 (strong) and 2108 cm^–1 (very weak) (CO) IR bands due to Cu⁺–CO in ZSM-5 zeolite with ¹²C and ¹³C isotopes, respectively, are reversibly red-shifted by subsequent adsorption of H₂O at 293 K. On the contrary, the locally perturbed internal (T–O–T) asymmetric stretching framework vibration [ _as ^int (TOT)(Cu⁺–CO)=965 cm^–1] is reversibly blue-shifted. The courses of the band shifts revealed notable features. Charge transfers from water to Cu⁺ ions, changes in coordination spheres of Cu⁺(CO)(H₂O) _n aqua complexes and secondary (solvent-like) effects were considered to explain the results.     

Reduction Characteristics of Iodate Ion on Copper: Application to Copper Chemical Mechanical Polishing

Potentiodynamic and potentiostatic polarization, and the rotating disk electrode technique were used to study the reduction characteristics of iodate (IO₃ ^–) ion on copper (Cu). Depending on the relative concentrations of IO₃ ^– and H⁺ two pH regimes were observed. The cathodic current in the first regime (pH > ,3) was controlled by H⁺ diffusion from the solution to the metal surface. In the second regime (pH > 3 and up to 10^–2 m IO₃ ^– concentration) the cathodic current was found to be under mixed control, involving reaction control via the electrochemical reduction of IO₃ ^– and transport control via the diffusion of I₂(aq). It was concluded that IO₃ ^– was an effective oxidant for Cu chemical mechanical polishing (CMP) with strongly acidic (pH < 3) slurries but it was not convenient reagent as an oxidant for Cu CMP with weakly acidic (pH > 3) slurries.     

The effect of benzotriazole on mass transfer in the corrosion of a copper rotating disk electrode

The effect of benzotriazole, BTA, on mass transfer in dissolution-corrosion of the copper rotating disk electrode in 0.02 M Fe(III)–0.5 M H₂SO₄ has been studied by means of atomic absorption spectrometry. The mass transfer coefficient, K, was determined from the slope of ln(C ₀/C)_Fe(III) vs. time plots. In the absence of BTA the corrosion process can be described by the correlation Sh = KR/D = 4.47Re ^0.5. The difference in values between Sh and Sh _Levich, and the change in slope in the Arrenhius plot points to mixed control for the cathodic process Fe³⁺ + 1e^– Fe ²⁺ and charge transfer control for the anodic process, Cu Cu²⁺ + 2e. The average activation energies were 7.7 kJ mol^–1 and 19.5 kJ mol^–1 at (500–1500) and (2000–3000) rpm, respectively. At low concentration of BTA the inhibiting action of BTA increases with concentration and with rotation speed. For [BTA] 5 × 10^–3 M, the K value, 10^–4 cm s^–1, remains constant and is independent of rotation rate. The morphology of the copper rotating disk after corrosion in the absence and presence of BTA was examined using scanning electron microscopy (SEM).     

Bio-inspired chemical hydrogen storage and discharge as a source of electrical energy

Reversible bio-inspired chemical hydrogen storage systems accumulate electrical energy in the form of electrons and proton ions located on biomolecules or bio-like storage molecules. Electro-active biomolecules (EAB) in Yeast media show such behavior: 2e⁻ + 2H⁺ + EAB_(aq)⁺ ⇆ EABH/H_(aq)⁺, also electro-active Methylene Blue (MB): 2e⁻ + 2H⁺ + MB_(aq)⁺ ⇆ MBH/H_(aq)⁺. The power characteristics of microbial fuel cell stacks equipped with such bio-inspired hydrogen storage systems were examined. E. coli cultures charged these bio-inspired separate chemical hydrogen storage units up to E = 0.50 ± 0.06 V; cell potentials increased proportionally in serial double, triple, and quadruple hydrogen storage stacks up to E _OCV = 1.98 V; the maximum power densities that were obtained improved proportionally with stack length by an increment of 1.4. The bio-inspired chemical hydrogen storage principle is of great interest for application in low-cost batteries that store renewable energy.     

Removal of Chromium and Organic Pollutants from Industrial Chrome Tanning Effluents by Electrocoagulation

The treatment of industrial chrome tanning effluents by electrocoagulation (EC) in a laboratory‐scale reactor was investigated. Mild‐steel (MS) electrodes have been found to outperform aluminum (Al) electrodes in reducing the Cr(III) concentration to <2 mg L^–1. The conversion of Fe(II) to Fe(III) is slow in the lower pH range (<6), and OH^– ions generated during EC are amply available for Cr(III) removal by precipitation in the case of the MS electrode. Formation of Al(OH)₃(s) in competition with Cr(OH)₃(s) while consuming the OH^– ion is a cause for lower Cr(III) removal with Al. EC with the MS electrode and chemical coagulation (CC) with addition of alkali proved to be equally efficient for removing Cr(III).     

Preparation of a pigment in the Cr(III)-Co(II)-NO3-H2O system

Joint precipitation of Cr(III) and Co(II) ions at pH = 1.8–12.0 and 2.5–12.0 is investigated. It is established that a Cr₂Co₃O₆ · 10H₂O hydrocomplex precipitates in the Cr(III)-Co(II) -NO₃- H₂O system at pH = 3.0 –10.5 and is dehydrated at 940°C. The compound obtained can be used as a pigment for preparing overglaze paints and color glazes for decorating porcelain, faience, and majolica articles.Translated from Steklo i Keramika, No. 10, pp. 23–24, October, 1995.     

Modeling an electrochemical process to remove Cr(VI) from rinse‐water in a stirred reactor

Experimental studies were developed in a batch reactor (16 dm³), to obtain the kinetic model of Cr(VI) removal by means of an electrochemical process. An overall kinetic model was obtained and experimentally validated in a continuous stirred electrochemical reactor (16 dm³) with synthetic and industrial wastewater. To develop the mathematical model of the continuous reactor in relation to the Cr(VI) and Fe(II) concentration in the solution, a classical mass balance procedure was performed. The Cr(VI) concentration in the electrochemically‐treated waters was less than 0.5 mg dm^?3. In the electrochemical process the Cr(VI) reduction is caused by the Fe(II) released from the anode due to the electric current applied, by the Fe(II) released for the dissolution (corrosion) of the electrodes due to the acidic media, and by reduction at the cathode. During the process, reduction from Fe(III) to Fe(II) occurs. All of these different reactions cause a diminution in the quantity of sludge generated. Finally, it was found that due to the slow rate of reduction of Cr(VI) during the first part of the process it is necessary to develop a method of control to apply the process in a continuous industrial system. © 2003 Society of Chemical Industry     

Correlation between the electrochemical properties of colloidal oxides and supported oxides on metallic substrates

Mixed oxide electrodes of Ti(IV) and Cr(III) were prepared by calcining Cr(OH)₃ layers deposited on metallic titanium supports. This treatment produced a mixed oxide film of TiO₂–Cr₂O₃ covered with a layer of pure Cr₂O₃. The electrochemical response (cyclic voltammetry) shows the presence of two or three oxidation peaks depending on the electrode preparation conditions. One peak may be interpreted as the oxidation of Cr(III) to Cr(VI) species and the appearance of other peaks is due to the presence of chromium atoms in oxidation states higher than (III). The results of chemical analyses, electrophoretic mobilities and acid-base potentiometric titrations on calcined Cr(OH)₃ powders shows that the calcination step in air produced the decomposition of the Cr(III) hydroxide to the Cr(VI) oxide. Soluble Cr(VI) compounds were found in equilibrium with the suspended powder oxide which markedly affected the shape of the titrations curves. From the amount of Cr(VI) present in solution it was possible to correct the experimental ₀-pH curves. These corrected data indicated that Cr(VI) soluble species adsorbed at the Cr₂O₃/electrolyte interface.     

Use of vivianite (Fe3(PO4)2.8H2O) to prevent iron chlorosis in calcareous soils

For various reasons, iron phosphate might be effective in correcting Fe chlorosis in calcareous soils. To test this hypothesis, several pot experiments were conducted using an Fe chlorosis-sensitive chickpea (Cicer arietinum L.) cultivar cropped in soils to which partially oxidized vivianites (Fe₃(PO₄)₂.8H₂O) and Fe(III) phosphates with different characteristics had been added. Vivianites mixed with the soil at a rate of 1 g kg^–1 were as effective in preventing chlorosis as Fe chelate (FeEDDHA). However, the effectiveness of Fe(III) phosphates was less, suggesting that the presence of Fe(II) in the phosphates used was a key factor in their Fe-supplying value to plants. The effectiveness of vivianites, however, seemed to be largely independent of their Fe(II) content.The future of vivianite as a Fe amendment will depend not only on economic considerations (production and application costs) but also on its long-term capacity to release plant-available Fe in soil environments.     

Decomposition of nitrous oxide over the catalysts derived from hydrotalcite-like compounds

Catalytic decomposition of nitrous oxide into nitrogen and oxygen has been carried out on ‘in situ' thermally calcined hydrotalcites of general formula M(II)–M(III)-CHT where M(II)=Mg, Co, Ni, Cu or Zn and M(III)=Al, Fe or Cr having different M(II)/M(III) atomic ratios. The reaction was performed in a recirculatory static reactor at 50 Torr (133.3 Pa) initial pressure of N₂O in the temperature range 423–773 K. Among the catalysts screened, Ni and Co containing catalysts with Al as the trivalent cation showed good activity (even at 423 K) wherein 50% and 100% conversion was achieved at 463 K and 523 K, respectively. Results on effect of composition for Co–Al system indicated that the activity increased with increase in the active metal ion concentration (Co²⁺), with closer dependence on the surface concentration (as determined by XPS). The observed activity pattern is explained on the basis of redox property and electronic effects. These materials were further evaluated under flow conditions (at Air Products and Chemicals, USA) simulating the industrial process streams (10% N₂O, 2% H₂O, 2% O₂ and balance N₂ and GHSV=18,500). Among the non-precious metal ions investigated, cobalt-based catalysts offered comparable activity similar to metal-exchanged zeolites for removing N₂O from combustion and Nylon-6,6 processes.     

Electrosynthesis of cobalt (III) ions in concentrated H3PO4 medium

The electrosynthesis of cobalt(III) ions from cobalt(II) ions has been studied in 29, 57 and 85 wt % H₃PO₄ solutions. It has been shown that the conversion of Co(II) to Co(III) is limited by the chemical reaction between Co(III) ions and water. A kinetic study demonstrated that this reaction becomes more rapid as the Co(III) ion concentration increases. In order to find the best conditions for the electrolysis, the effect of some experimental parameters on the current yield and the chemical efficiency has been examined. A comparison between gold and platinum anodes has also been made. The following conditions were found to be the best: anode material, gold; initial Co(II) ion concentration, 5×10^–3 M; solvent, 85 wt % H₃PO₄ solution; current density, 1 mA cm^–2; temperature, 20–30° C. Under these conditions the maximum value of current yield, and chemical efficiency are 66% and 48% respectively.

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Résumé L'electrosynthèse des ions cobalt(III) à partir des ions cobalt(II) a été étudiée dans les solutions H₃PO₄ 29, 57, et 85% en masse. II a été montré que la conversion de Co(II) en Co(III) est limitée par la réaction chimique entre les ions Co(III) et l'eau. Une étude cinétique a montré que cette réaction devient plus rapide au fur et à mesure que la concentration de l'ion Co(III) augmente. Dans le but de trouver les conditions favorables pour l'electrolyse, l'effet de certains paramètres expérimentaux, sur les rendements électrique et chimique, a été examiné. Les résultats obtenus avec une anode en or et une anode en platine ont été comparés. Les conditions d'électrolyse suivantes ont été retenues: le matériau de l'anode, Au; concentration initiale de l'ion Co(II), 5×10^–3 M; solvant, solution H₃PO₄ 85% en masse; densité de courant, 1 mA cm^–2; température, 20–30° C Dans ces conditions, les valeurs des rendements faradique et chimique maximum sont respectivement de 66% et 48%.

     

An unusual dichromium(II,II) compound bearing di-2-pyridyl ketone oximate ligands and prepared by the ligand-assisted reduction of a trichromium(III,III,III) complex in air

The reaction of the oxide-centred triangular, trichromium(III,III,III) complex [Cr₃O(O₂CCMe₃)₆(H₂O)₃](O₂CCMe₃) with di-2-pyridyl ketone oxime, (py)₂CNOH, in MeCN under aerobic and refluxing conditions yields the pivalate-free, dichromium(II,II) complex [Cr₂{(py)₂CNO}₄] · 2H₂O (1 · 2H₂O). The dinuclear complex can also be prepared by the reaction of [Cr(CO)₆] with (py)₂CNOH in refluxing MeCN/H₂O in air. The two high-spin Cr^II atoms are doubly bridged by two 2.1110 oximate ligands, while a chelating 1.0110 (py)₂CNO⁻ ion completes distorted trigonal bipyramidal coordination at each metal centre. The dimers are stabilized by intramolecular stacking interactions between the terminal (py)₂CNO⁻ ligands, and the structural effects of these interactions are discussed.     

Sorption and Magnetic Properties of Oxalato-Based Trimetallic Open Framework Stabilized by Charge-Assisted Hydrogen Bonds

We report a new structure of {[Co(bpy)₂(ox)][{Cu₂(bpy)₂(ox)}Fe(ox)₃]}_n·8.5nH₂O NCU-1 presenting a rare ladder topology among oxalate-based coordination polymers with anionic chains composed of alternately arranged [Cu₂(bpy)₂(ox)]²⁺ and [Fe(ox)₃]³⁻ moieties. Along the a axis, they are separated by Co(III) units to give porous material with voids of 963.7 ų (16.9% of cell volume). The stability of this structure is assured by a network of stacking interactions and charge-assisted C-H…O hydrogen bonds formed between adjacent chains, adjacent cobalt(III) units, and alternately arranged cobalt(III) and chain motifs. The soaking experiment with acetonitrile and bromobenzene showed that water molecules (8.5 water molecules dispersed over 15 positions) are bonded tightly, despite partial occupancy. Water adsorption experiments are described by a D’arcy and Watt model being the sum of Langmuir and Dubinin–Serpinski isotherms. The amount of primary adsorption sites calculated from this model is equal 8.2 mol H₂O/mol, being very close to the value obtained from the XRD experiments and indicates that water was adsorbed mainly on the primary sites. The antiferromagnetic properties could be only approximately described with the simple Cu^II-ox-Cu^II dimer using H = −J·S₁·S₂, thus, considering non-trivial topology of the whole Cu-Fe chain, we developed our own general approach, based on the semiclassical model (SC) and molecular field (MF) model, to describe precisely the magnetic superexchange interactions in NCU-1. We established that Cu(II)-Cu(II) coupling dominates over multiple Cu(II)-Fe(III) interactions, with J_CuCu = −275(29) and J_CuFe = −3.8(1.6) cm⁻¹ and discussed the obtained values against the literature data.