Electrochemical synthesis of Cr(II) at carbon electrodes in acidic aqueous solutions

The electrochemical synthesis of Cr(II) has been investigated on a vitreous carbon rotating disc electrode and a graphite felt electrode using cyclic voltammetry, impedance spectroscopy and chronoamperometry. The results show that in 0.1 M Cr(III) + 0.5 M sulphuric acid and in 0.1 M Cr(III) + 1 M hydrochloric acid over an electrode potential range of –0.8 to 0.8 V vs SCE, the electrochemical reaction at carbon electrodes is essentially a surface process of proton adsorption and desorption, without significant hydrogen evolution and chromium(II) formation. At electrode potentials more negative than –0.8 V vs SCE, both hydrogen evolution and chromium(II) formation occurred simultaneously. At electrode potentials –0.8 to –1.2 V vs SCE, the electrochemical reduction of Cr(III) on carbon electrodes is controlled mainly by charge transfer rather than mass transport. Measurements on vitreous carbon and graphite felt electrodes in 1 M HCl, with and without 0.1 M CrCl₃, allowed the exchange current density and Tafel slope for hydrogen evolution, and for the reduction of Cr(III) to Cr(II), to be determined. The chromium(III) reduction on vitreous carbon and graphite electrodes can be predicted by the extended high field approximation of the Butler–Volmer equation, with a term reflecting the conversion rate of Cr(III) to Cr(II).     

Chromium redox couples for application to redox flow batteries

Both anodic and cathodic chromium-EDTA (ethylenediaminetetra-acetate) complex redox processes have been studied using cyclic voltammetry. Their potential use in a redox battery has been evaluated by comparing the charge and discharge performance of a simple redox battery employing several redox couples including the conventional Fe-Cr redox couples. The cyclic voltammetry experiments suggested that oxidation of Cr(III)-EDTA formed Cr(V)-EDTA rather than a hexavalent chromium species. It was found that the kinetics of the Cr(III)-EDTA/Cr(II)-EDTA redox reaction are fast at a graphite rod electrode, whereas the Cr(V)-EDTA/Cr(III)-EDTA redox reaction is relatively slow. In spite of the slow kinetics, the battery employing solely these chromium-EDTA based redox couples provided higher energy output and longer life than the conventional Fe-Cr redox system.     

Morphology and composition of the Fe-Ni powders electrodeposited from citrate containing electrolytes

The electrodeposition of the Fe-Ni powders from citrate containing electrolytes for different Ni/Fe ions concentration ratios, using Fe(III) and Fe(II) salts at pH 4.5 and pH 4.0 respectively was investigated by the polarization measurements and cyclic voltammetry. The morphology and composition of the electrodeposited powders were investigated by SEM and EDS analysis. The EDS analysis of the alloy powders confirmed anomalous co-deposition of Fe and Ni from both solutions, with the one obtained using Fe(III) salt being more pronounced. The morphology of electrodeposited powders was found to depend on the Ni/Fe ions concentration ratio, as well as on the valence of Fe ions used. A common characteristic for all powder samples was the presence of cone shaped cavities and nodules, while for the ratio Ni/Fe = 9/1 in both electrolytes pagoda like crystals, corresponding to the FeNi₃ single crystal, have been detected. In the case of Fe(III) containing electrolytes current efficiency for powder electrodeposition was very small (about 1-2%) due to the first step in the electrochemical reaction being reduction of Fe(III) into Fe(II), while in the case of Fe(II) containing electrolytes current efficiency for powder electrodeposition varied between about 15% and 8% depending on the Ni/Fe ratio.     

电沉积纳米晶镍-铁-铬合金

采用直流和脉冲电沉积方式从三价铬的氯化物镀液中沉积出镍-铁-铬纳米合金镀层，利用扫描电镜分析镀层形貌及晶粒尺寸，研究了沉积速率，电流效率，三价铬浓度及pH值随沉积时间的变化关系，结果表明，脉冲电沉积所得镀层的结构和性能均优于直流电沉积，这是由于脉冲电沉积存在断电时间，使得电极表面扩散层中金属离子的浓度得到及时恢复。     

Effect of Cr(III) solution chemistry on electrodeposition of chromium

This work provides a new insight into the interaction of urea with formate during the chromium electrodeposition from a sulphate-based Cr(III) solution. The influence of solution chemistry on chromium electrodeposition in a Cr(III) bath containing sodium formate and urea as complexing agents was studied by FT-IR, XPS and AFM. The results show that good quality Cr coatings may be obtained only in those cases when the secondary ligand with the carbamidic group predominates over urea in the electrolyte. This suggests that electrodeposition of good quality chromium deposit is possible due to the formation of active chromium–carbamid complexes [Cr(carbamid)_n(H₂O)_6-n ]³⁺. These complexes delay the formation of the stable oligomeric species, and thus provide a prolonged working lifetime in the Cr(III) formate-urea electrolyte.     

铁氧体法去除废水中的镍、铬、锌、铜离子

采用铁氧体法处理含镍、铬、锌、铜的废水,研究了pH及硫酸亚铁投加量对重金属离子去除效果的影响.对于镍、锌、铜离子,最佳絮凝pH分别为8.00～9.80、8.00～10.50和10.00,投加的亚铁离子与其摩尔比均为2～8;六价铬的最佳还原pH为4.00～5.50,最佳絮凝pH则为8.00～10.50,最佳投料比为20....     

The electrodeposition of chromium from chromium(III) solutions — a study using microelectrodes

Potential sweep and pulse experiments at a carbon microdisc electrode (radius 4 m) have been used to investigate chromium plating from aqueous solutions of chromic ions containing sulphate or thiocyanate ions and buffered at pH 3.3. While chromium deposition occurs in many media, it is shown that the plating reaction is always in competition with other cathodic reactions including hydrogen evolution. This leads to loss in current effciency and, in some circumstances, to precipitation of chromic hydroxide on the cathode and, hence, contamination of the metal. In addition, it is demonstrated that the chromium(III) exists in solution as mixtures of complexes, not all of which are electroactive within the accessible potential range. Hence the investigation confirms that the quality of electroplates will vary strongly with the choice of medium. A commercial chromium(III) plating bath, Envirochrome, has also been studied and it is concluded that its properties are superior to simple sulphate or thiocyanate solutions.     

Properties and preparation of amorphous chromium carbide electroplates

The electrochemical and corrosion behavior of chromium electroplates formed in sulfuric acid solutions of Cr(III) in the presence of oxalates was studied by measuring steady-state polarization curves in 0.5 M H₂SO₄ solution. These electroplates demonstrate no active dissolution region and their open-circuit potentials are located in the passivity region, i.e. shifted substantially in the positive direction as compared with those of metallurgical chromium and electroplates from standard chrome-plating baths. The results of X-ray photoelectron spectroscopy (XPS) studies evidence that the passive metal surface layer several nanometers thick consists of chromium oxides with incorporated carbides formed during electroplating. It is supposed that the peculiarities of the corrosion and electrochemical behavior of the deposits under study can be attributed to the presence in them of chromium carbides, which operate as cathodic agents. At the same time, the formation of these carbide compounds during the cathodic deposition of chromium electroplates from sulfuric acid Cr(III) solutions in the presence of sodium oxalate is a result of electrocatalytic activity of metal chromium. The latter assumption is confirmed by XPS analysis of surface layers formed during the exposure of chromium to sulfuric acid solutions containing organic substances.     

Oxalic acid catalysed chromium(VI) oxidation of some 2-amino-4,6-diarylpyrimidines

Some 2-amino-4,6-diarylpyrimidines (APM), synthesized from chalcones and guanidine hydrochloride in presence of alkali by microwave irradiation in solvent-free conditions, were subjected to oxidation with chromium(VI)–oxalic acid complex (Cr(VI)–Oxa) in highly acidic solutions. Oxalic acid (Oxa) offers the reaction a more favourable pathway and in the absence of oxalic acid the reaction is sluggish. The depletion of chromium(VI) shows a complicated kinetics involving a fast reaction to about 35% consumption followed by a slow one. Low dielectric constant of the medium facilitates the reaction. The investigations with 2-amino-6-(4-nitrophenyl)- 4-phenylpyrimidine and 2-amino-6-(4-methoxyphenyl)-4-phenylpyrimidine reveal that, irrespective of the nature of the substituents, the rates are higher than for the parent. APM is catalytically converted to the unusual product 3-hydroxy-1,3-diphenyl-propan-1-one. Consideration of the kinetic behaviours under different experimental conditions and the product assignment provide valuable mechanistic insight into the system studied.     

Phenolic and tannin-based adhesive resins by reactions of coordinated metal ligands. I. Phenolic chelates

Bivalent and trivalent metallic ions, respectively, accelerate and inhibit the reaction of phenols with formaldehyde. The catalytic effect of these metallic ions is equivalent, though more marked, to that of hydrogen ions, and it is due to their stronger charge. Metallic ions/phenols/formaldehyde complexes are formed. The stability of these complexes and mainly their rate of metal exchange in solution are the determining factors in the accelerating or retarding action. Identified stable chromium (III)–resorcinol–formaldehyde and chromium (III)–phenol–formaldehyde complexes have slow rates of metal exchange and inhibit the resorcinol–formaldehyde and phenol–formaldehyde reactions. The opposite is valid for lead (II), zinc (II), and other bivalent metallic ions. A scale showing the order of the accelerating effect of a series of metallic ions is given. The presence of polymeric complexes has also been observed.     

A systematic study of chromium solubility in the presence of organic matter: consequences for the treatment of chromium‐containing wastewater

The treatment objective for wastewater containing Cr(VI) and/or Cr(III) is the reduction of Cr(VI) to the less toxic Cr(III) and the sequestering of Cr(III) from the water streams. The presence of organic matter in the wastewater and in a bioreactor environment may alter the solubility behavior of Cr(III), resulting in poor sequestering and Cr(III) removal from the soluble phase. Systematic experimental solubility results for Cr(III) were obtained in the presence of organic molecules often encountered in industrial effluents containing chromium as well as in biological treatment systems. Chromium solubility curves were determined experimentally from synthetic solutions of Cr(III) in contact with organic acids (acetic, oxalic, citric and ascorbic), amino acids (alanine and aspartic), proteins (albumin and casein) and synthetic nutrient media (yeast extract, nutrient broth and peptones). Experimental data sets were generated for each one of the above organics at three different initial organics concentrations in order to quantify the role of the relative abundance of organic matter in the solubility behavior of Cr(III). A progressive increase of trivalent chromium solubility was systematically observed when the relative abundance of organic ligands to Cr(III) exceeds 10, indicating the existence of a threshold above which the solubility of Cr(III) increases significantly. The hexacoordinate and octahedral character of Cr(III) complexes may explain the need for ligand excess also pointing to a treatment strategy suggesting the relative abundance of organic moieties should be kept below the above threshold. Copyright © 2007 Society of Chemical Industry     

Interaction of lead and chromium with chitin and chitosan

The interaction of the natural marine polymer chitin and its deacetylated derivative chitosan with lead and chromium has been investigated. The uptake of lead and chromium was determined from changes in concentration as measured by atomic absorption spectroscopy. A significant uptake of Pb(II) on both chitosan and chitin was observed. However, the uptake of Pb(II) on chitin was approximately 21% of that on chitosan. The number of Natoms in chitin and chitosan and per number of Pb(II) ions sorbed was 115 and 29, respectively. The number density of flakes observed in the scanning electron microscope and characterized by an intense Pb signal in energy dispersive analysis of x rays (EDAX) was greater on the surface of chitosan [containing 1.7 × 10^?4 mole Pb(II)/g chitosan] than chitin [containing 3.5 × 10^?5 mole Pb(II)/g chitin] after equilibration with Pb(II) solution. The bonding state of lead on chitosan as determined by electron spectroscopy for chemical analysis (ESCA) is similar to the bonding of lead in PbO based on the Pb 4f_7/2 binding energy. A significant shift in the O 1s binding energy from 532.2 to 531.4 eV was observed for chitosen after equilibration with Pb(II) solution. The caculated values of the N/Pb ratio from ESCA spectra were 0.5 and 11, for chitosan and chitin, respectively. A significant uptake of Cr(III) on chitosan was observed and a significant increase in the pH of solutions of Cr(III) on equilibration with chitosan occurred. A high number density of nodules characterized by an intense Cr signal in EDAX was observed in chitosan [containing 2.5 mole Cr(III)/g chitosan] after equilibration with Cr(III) solution. The calculated values of the N/Cr ratio from ESCA spectra was 18 for chitosan.     

Chromium electrodeposition from [BMIm][BF<Subscript>4</Subscript>] ionic liquid

The electrodeposition of black chromium coatings from ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate with chromium chloride, and the chemical composition of the deposits are discussed in this article. The UV–Vis spectra recorded for chromium(III) species in 1-butyl-3-methylimidazolium tetrafluoroborate suggest that along with the chromium(III) complexes containing three ligands, there are some amounts of chromium species containing four ligands in the bath employed. The cathodic process of chromium electrodeposition in the employed ionic liquid is complicated by the electrochemical reduction of water molecules, which is followed by chemical disintegration of tetrafluoroborate ions. The surface morphology of black chromium films deposited potentiostatically (–1.5 to −2.0 V) at 85 °C shows nodules and microcracks increasing in size with cathodic potential. Analysis of the X-ray photoelectron spectra recorded from surface to depth of the deposit has shown that the black oxide-rich chromium coating consists of chromium in both oxide and metallic states with small impurities of other elements (fluorine, boron, carbon and nitrogen) and the surface is covered with a thin layer of organic substances. The results of this study show that 1-butyl-3-methylimidazolium tetrafluoroborate may be considered as a promising substitute of toxic Cr(VI) baths for black chromium plating.     

Kinetics and mechanism of the anodic dissolution of nickel in HCl-dimethylsulphoxide solutions

The anodic dissolution of nickel in HCl-DMSO solutions containing different supporting electrolytes has been studied between 20–40°C. The electrodissolution and electrodeposition are predominantly activated electrode processes. At high anodic potentials and in the presence of perchlorate ions at high concentration passivation sets in.A probable reaction pathway is postulated which explains most of the experimental findings. Passivation corresponds to a salt precipitation-dissolution process at the electrode vicinity.     

Improvement of passivity of Fe–<Emphasis Type="Italic">x</Emphasis>Cr Alloys (<Emphasis Type="Italic">x</Emphasis> < 10%) by cycling through the reactivation potential

Classically, 13% Cr is required for stable passivity of a Fe–Cr alloy in acidic and neutral solutions not containing inhibitors. Some authors (Mansfeld, Fujimoto) have published potential cycling procedures that generate thick Cr-rich films. In this work, a similar technique, but with a far smaller potential cycle, was used to enrich a surface layer in chromium, thereby increasing corrosion-resistance in otherwise non-passivating steels. This was achieved by potential stepping across the iron reactivation potential, firstly forming passive iron(III) oxide, then reducing it to soluble iron(II) ions, while ensuring the passivity of chromium. The use of potential stepping was found to result in a more robust film than that formed through a single continuous passivation step.     

The use of organic acids as precipitants for metal recovery from galvanic solutions

The abundance of metal ions in galvanic waste solutions enables these solutions to be used for recovery of metals as well as complexing agents such as citrate and tartrate. The addition of oxalic acid to solutions containing complexing agents precipitates pure metal oxalate or mixtures of metal oxalate and tartrate or citrate, the product depending on pH and concentration of components. The addition of oxalic acid to the rinsing bath after electroplating precipitates the most of the metals such as Cu(II), Zn(II) and Pb(II). ©1997 SCI     

Removal of chromium(III) from tannery effluents,using a system of packed columns of zeolite and activated carbon

The removal of chromium(III) in packed columns of zeolite and activated carbon has been studied. The process of Cr(III) exchange in 13X zeolite was optimized using mass transference parameters. In addition, the effects of pH, the presence of interfering ions and the anion associated with the chromium in the solution were studied. It was found that particle diameter controls the Cr(III) exchange in the zeolite, indicating that particle diffusion predominantly controls the process of Cr(III) exchange in 13X zeolite. A mixed system of zeolite and activated carbon columns increased the efficiency of chromium removal from diluted wastewater. This effect occurred due to the reduction of the organic matter (chemical oxygen demand), adsorption of chromium, and interfering ions on the activated carbon column. The activated carbon + zeolite column system emerges as an alternative method in Cr(III) removal from tannery effluents. Copyright © 2005 Society of Chemical Industry     

The diffusion coefficient of Cu(II) ions in sulfuric acid–aqueous and methanesulfonic acid–methanol solutions

When using a copper working electrode to study the diffusion of Cu(II) ions it is necessary to polish the electrode between experiments to maintain a smooth surface. To eliminate the required polishing, a platinum working electrode can be used. The copper layer established on the electrode surface during experimentation can be removed between experiments by anodic stripping. When using a platinum disk working electrode, the most reliable method of analysis involves double potential step chrono-amperometry method as opposed to voltammetry. By applying this method diffusion coefficients for Cu(II) ions in sulphuric acid – aqueous and methanesulfonic acid (HMSA) – methanol solutions were determined.     

Selective removal of some heavy metal ions from aqueous solution using treated polyethylene-g-styrene/maleic anhydride membranes

Radiation graft copolymerization of styrene/maleic anhydride (Sty/MAn) comonomer onto low density polyethylene (LDPE) membrane was investigated. The prepared grafted membranes were treated with different reagents containing various functional groups and studied as a matrix for the purpose of water purification from heavy metals. The metal ion uptake by the functional groups of membranes was determined by the use of X-ray fluorescence (XRF) and atomic absorption (AA). The effect of pH of the metal feed solution and immersion period needed for maximum capacity was investigated. The selectivity of different prepared membranes towards some selected metal ions such as Fe, Cu, Pb,… etc. which commonly exist in waste water was determined. The affinity of the treated grafted films to recover Fe(III), Cu(II) or Pb(II) from their aqueous solutions containing other metal ions such as Cd(II), Ni(II) or Hg(II) was studied. Also the selectivity of treated grafted membranes towards Cu(II), Cr(III) and Fe(III) in a mixture was investigated at room temperature and 70°C. It was found that the thiosemicarbazide-, hydroxylamine·HCl- and NaOH-treated grafted films showed high selectivity towards Cu(II), Cr(III) and Fe(III), respectively, at 70°C. However, the selectivity of such treated grafted membranes was remarkable towards Fe(III) at room temperature. The results obtained suggested that the treated grafted membrane possessed good chelating properties towards different metal ions. This suggests that such membranes could be accepted for practical uses.     

用恒电流法研究Fe（Ⅲ）EDTA对银的氧化过程

本文采用银旋转圆盘电极,在氟离子、溴离子、碘离子以及其他照相辅加剂存在下对Fe(Ⅲ)EDTA氧化金属银的过程进行了研究,以恒电流法做为检测手段,初步探讨了Fe(Ⅲ)EDTA络合物对金属银漂白过程机理。实验揭示了各种卤离子在Fe(Ⅲ)EDTA对银的氧化过程中的行为。pH和Fe(Ⅲ)EDTA浓度对该氧化还原反应的影响,以及某些含有巯基的化合物对Fe(Ⅲ)EDTA氧化反应的加速作用机理。