Kinetics and mechanism of chromium electrodeposition from formate and oxalate solutions of Cr(III) compounds

Kinetics of multistep reaction of Cr(III) ions discharge to metal was studied on a stationary electrode and on a rotating disk electrode from the solutions containing formic acid or oxalic acid. The electroreduction of Cr(III) complex ions in aqueous solutions is shown to proceed via the formation of relatively stable intermediates—Cr(II) compounds which are partially removed into bulk solution. The effect of pH, organic ligand concentration and disk rotation velocity on the partial current density of chromium electroplating was demonstrated. The kinetic equations of the studied process were derived and compared with the experimental data. Kinetic parameters for the discharge of Cr(II) ions were calculated. The mechanism of chromium electrodeposition reaction was proposed. The electrodeposition of chromium from formate bath is suggested to proceed with the participation of hydroxocomplexes of bivalent chromium. The oxalate complexes of bivalent chromium directly discharge in the electrolytes containing oxalic acid. The partial polarization curves of chromium electrodeposition exhibit a current peak which may be caused by blocking the electrode surface with poorly soluble Cr(III) hydroxide.     

Removal of Ni(II) ions from wastewater by micellar enhanced ultrafiltration using mixed surfactants

Ni(II) ions were removed from aqueous waste using micellar enhanced ultrafiltration (MEUF) with a mixture of surfactants. The surfactant mixture was the nonionic surfactant Tween 80 (TW80) mixed with the anionic surfactant sodium dodecyl sulfate (SDS) in different molar ratios ranging from 0.1–1.5. The operational variables of the MEUF process such as pH, applied pressure, surfactant to metal ion ratio and nonionic to ionic surfactant molar ratio (α) were evaluated. Rejection of Ni and TW80 was 99% and 98% respectively whereas that for SDS was 65%. The flux and all resistances (fouling resistance, resistance due to concentration polarization) were measured and calculated for entire range of α respectively. A calculated flux was found to be declined with time, which was mainly attributed to concentration polarization rather than resistance from membrane fouling.     

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     

胶团强化超滤在处理重金属离子废水中的应用

本文介绍了一种具有表面活性荆双分子结构特性的新型重金属离子废水处理技术一胶团强化超滤（Micellar—enhanced Ultrafiltration，简称MEUF）。MEUF适用于单独或同时从废水中去除多价金属离子，具有工艺简单，易于工业化的特点。文章介绍了胶团强化超滤的原理、主要影响因素、存在的问题及解决方法，总结了近年来胶团强化超滤应用的最新研究成果，认为该技术具有良好的应用前景。     

Adsorption of Cr(VI) on Cross‐Linked Chitosan Beads

Abstract

A possibility of Cr(VI) removal by the adsorption method is discussed in the paper. An adsorbent were hydrogel chitosan beads are produced by the phase inversion method (by changing pH). The possibility of removing Cr(VI) ions by both pure chitosan hydrogel and its chelate compounds (chitosan cross‐linked with Cu(II) and Ag(I) ions) was investigated. The adsorption proceeded from the solutions of potassium dichromate and ammonium dichromate (NH₄)₂Cr₂O₇ and K₂Cr₂O₇. The process rates and adsorption isotherms were determined and described by relevant equations. The process rate was described by the pseudo‐ and second‐order equations, and adsorption equilibria by the Langmuir equations. A slight advantageous change in adsorption properties of chitosan beads was revealed after cross‐linking (for chromium concentration up to 10 g/dm³). A maximum adsorption was 1.1 g_Cr/g chitosan. Results of the studies show that chitosan hydrogel proves useful in the removal of Cr(VI) ions, additionally, cross‐linking with Cu(II) and Ag(I) ions has an advantageous effect in the case of low‐concentrated solutions.     

The kinetics and mechanism of the electroreduction of Bi(III) ions from chlorates (VII) with varied water activity

The influence of water activity on the mechanism and kinetics of Bi(III) ions electroreduction at dropping mercury electrode in chlorates (VII) using voltammetric and impedance methods was examined. The kinetic parameters determined in the examined solutions were correlated with water activity. The values of transfer coefficients, standard rate constants and activation energy point at the slight influence of supporting electrolyte concentration on the kinetics of Bi(III) electroreduction in 1-3 mol dm⁻³ chlorates (VII). In the concentration range of 4-8 mol dm⁻³ the values of transfer coefficients and standard rate constants increase considerably, whereas the values of activation energy decrease what testifies to the increase of reversibility of Bi(III) ions electroreduction. The character of the rate constants changes in the function of potential points at multi-stage process of Bi(III) ions electroreduction as well as a different mechanism of Bi(III) electroreduction in the solutions with low water activity in comparison with the solutions with high water activity.     

Influence of operating parameters on chromic ions removal from aqueous solution by liquid membranes

This paper presents the possibility of using liquid membranes as a separation and concentration technique to facilitate the recovery of Cr(VI) from water. Chromium(VI) being highly carcinogenic and mutagenic, it is necessary for risk assessment to remove and concentrate it in order to re-use it instead of reducing Cr(VI) to Cr(III). A separation scheme has been designed, using liquid membranes and rotating disk modules as contactors. Separation and enrichment can be simultaneously achieved in the same apparatus. Four operation parameters are considered : rotating disks speed, flow rate of chromium solution, initial chromium concentration and membrane volume. Experiments are performed in continuous mode. Estimation of the mass transfer coefficients is performed using macroscopic mass balances.     

Adsorption of Cr(III) ions by Turkish brown coals

The equilibrium and kinetic properties of Cr(III) ion adsorption by two brown coals from Anatolia, Turkey, have been investigated in batch stirred-tank experiments. The effects of adsorbent dose, initial sorbate concentration and contact time on the adsorption of Cr(III) by Isparta-Yalvaç-Yarikkaya (YK) and Kasikara (KK) brown coals were evaluated. The Cr(III) ions are able to form complex compounds with carboxylic and phenolic groups of brown coals and they were also bounded with phenolic groups even at low pH reaction of the solution (<3). Mechanisms including ion exchange, complexation and adsorption to the surface are possible in the sorption process. Our batch adsorption studies show the equilibrium adsorption data fit the linear Langmuir adsorption isotherm. Adsorption equilibrium was achieved in about 15–20 min for chromium(III). The Langmuir adsorption isotherm was used to describe the observed sorption phenomena. The maximum equilibrium uptake was 0.05 mmol of Cr(III)/g for KK, and 0.26 mmol of Cr(III)/g for YK, respectively, at a pH of 4.5. More than 90% of chromium(III) was removed by KK and YK from an aqueous solution after 60 min. In every experiment, the maximum Cr(III) was sequestered from the solution within 60 min. It is proposed that KK and YK brown coals can be used as potential sorbents for Cr(III) removal from aqueous solutions.     

Separation of Cr(VI) from Water by Green Reduction Reaction and Adsorptive Removal on Gelatin-Grafted-Yeast Biosorbent

A green chemical method was explored and described for separation and extraction of the toxic hexavalent chromium from aqueous solutions and real water samples. A green reduction reaction for the transformation of toxic hexavalent chromium into the nontoxic trivalent chromium ion was performed by using hydrogen peroxide. The produced Cr(III) was then extracted by biosorption on the surface of a novel and eco-friendly gelatin-grafted-baker’s yeast (Gelatin-Yeast) biosorbent. The investigated biosorbent was characterized by high capacity value of the reduced trivalent chromium species in pH 6.0 as 1.120 mmol g^?1. The biosorption processes were examined, monitored, and optimized in different experimental and controlling parameters. The potential applications of Gelatin-Yeast for separation and removal of Cr(VI) from real industrial and sea water samples were also studied.     

Study of sorption of chromium(VI) ions by fibre anion-exchangers

Sorption of chromium(VI) ions by fibre anion-exchangers containing pyridine, imidazole, hydrazidine, and aliphatic amino groups was investigated. It was shown that the basicity of the sorbents has almost no effect on their selectivity in absorption of chromium ions from solutions. The fibres with pyridine and imidazole groups have higher distribution coefficients, and their capacity for chromium ions is 130 and 120 mg/g, respectively. Sorption of chromium(VI) ions by the fibre sorbent with pyridine groups also corresponds to a mixed diffusion mechanism in dynamic conditions and the internal diffusion coefficient is 3.10 ⁻¹⁰ cm²/sec. Fibres with low-basicity pyridine groups are resistant to the oxidizing effect of chromium(VI) ions and their exchange capacity is preserved in repeated sorption-desorption cycles. Conversion of pyridine groups to the form of a strong base decreases the chemical stability of the sorbent in absorption of chromium(VI) ions from solutions. Translated from Khimicheskie Volokna, No. 2, pp. 55–57, March–April, 1997.     

Bioaccumulation and biosorption of copper(II) and chromium(III) from aqueous solutions by Pichia stipitis yeast

BACKGROUND: Bioaccumulation and biosorption by Pichia stipitis yeast has not yet been explored. This paper evaluates, for the first time, the use of both viable and nonviable P. stipitis yeast to eliminate Cu(II) and Cr(III) from aqueous solutions. The effect of Cu(II) and Cr(III) ions on the growth and bioaccumulation properties of adapted and nonadapted biomass is investigated as a function of initial metal concentration. Binding capacity experiments using nonviable biomass are also performed as a function of temperature. RESULTS: The addition of Cu(II) and Cr(III) had a significant negative effect on the growth of yeast. Nonadapted cells could tolerate Cu(II) and Cr(III) ions up to a concentration of 75 ppm. The growth rate of nonadapted and adapted cells decreased with the increase in Cu(II) and Cr(III) concentration. Adapted P. stipitis biomass was capable of removing Cu(II) and Cr(III) with a maximum specific uptake capacity of 15.85 and 9.10 mg g⁻¹, respectively, at 100 ppm initial Cu(II) and Cr(III) concentration at pH 4.5. Adsorption data on nonviable cells were found to be well modeled by the Langmuir and Temkin isotherms. The maximum loading capacity of dry biomass predicted from Langmuir isotherm for Cu(II) and Cr(III) at 20 °C were 16.89 and 19.2 mg g⁻¹, respectively, at pH 4.5. Biosorptive capacities were dependent on temperature for Cu(II) and Cr(III) solutions. CONCLUSION: Cu(II)‐ and Cr(III)‐adapted cells grow and accumulate these ions at high ratios. On the other hand, nonviable P. stipitis was found to be an effective biosorbent for Cu(II) and Cr(III) biosorption. Copyright © 2008 Society of Chemical Industry     

Application of multicomponent adsorption isotherms to simultaneous biosorption of iron(iii) and chromium(vi) on C. vulgaris

Although the biosorption of single metal ions to various microorganisms has been extensively studied and adsorption isotherms have been developed for single metal ion situations, very little attention has been given to the bioremoval and the expression of the adsorption isotherms of multi-metal ions systems. In this study, the competitive biosorption of iron(III) and chromium(VI) to Chlorella vulgaris from a binary metal mixture was studied and compared with the single metal ion situation in a batch stirred system. The effects of pH and single and dual metal ion concentrations on the biosorption rates and equilibrium uptakes were investigated. The optimum biosorption pH for both metal ions was determined as 2·0. Multi-metal ion biosorption studies were also performed at this pH value. It was observed that the biosorption rates and yields and equilibrium uptakes of iron(III) or chromium(VI) ions were reduced by the presence of increasing concentrations of the other metal ion. Adsorption isotherms developed for both single and dual metal ion systems at the optimum pH were expressed by the non-competitive and competitive Langmuir and Freundlich adsorption models, and model parameters were determined by computer. It was seen that the adsorption equilibrium data fitted very well to both of the models in the concentration ranges studied. ©1997 SCI     

OXIDATIVE TREATMENT FOR THE PREVENTION OF CHROMIUM ACCUMULATION IN A POLYMERIC MATRIX

ABSTRACT

Chromium (III) species tend to accumulate in the organic matrix with carboxylic groups like weak acid ion exchanger resins. Using conventional acidic solutions, chromium (III) can be partially eluted in some circumstances, while an oxidative stripping using hydrogen peroxide in alkaline media seems to be useful. Previously, Cr(III)–H₂O₂ reaction has been studied in aqueous solutions (homogeneous system) at 20°C, testing for 0.5, 1.0 and 2.0?mM of Cr(III) as total metal concentration. The effect of hydroxide ion on the rate of oxidation was also examined. Chromate was continuously monitored using an FIA system. The general mechanism of the homogeneous reactions has been postulated and the main kinetic parameters of the reactions have been calculated. Ageing of chromium (III) solutions has an important effect on the experimental results. Metal elution from cationic resin is usually carried out by strong acids, but here chromium loaded onto a cation-exchange resin is completely stripped after oxidation to chromate ion. The reaction rate is mainly controlled by intraparticular diffusion of the anionic species through the cationic resin. Surprisingly, these are not rejected from the resin phase by the Donnan exclusion. This apparently anomalous behaviour has been explained in terms of the reaction mechanism.     

Modeling and Performance Study of MEUF of Divalent Metal Ions in Aqueous Streams

Abstract

Modeling of micellar enhanced ultrafiltration (MEUF) was studied for the removal of Ni from aqueous phase by using sodium dodecyl sulphate for micellisation. Localized adsorption equilibrium model was used to predict the bound and unbound counter ions. The retentate concentration was predicted using localized adsorption equilibrium and a material balance model, and the experimental values are in close agreement with less than 1% deviations. Experimental values of the permeate flux were in close agreement with the predicted values obtained by resistances in the series model. An algorithm was developed for the prediction of the retentate concentration.     

Separation of Dissolved Phenolics from Aqueous Waste Stream using Micellar Enhanced Ultrafiltration

The micellar enhanced ultrafiltration (MEUF) process has been used for the separation of phenol and o-cresol from aqueous solutions at room temperature (30 + 2°C) using a cationic surfactant, cetyltrimethylammonium bromide (CTAB), and polyethersulfone membrane of molecular weight cut-off 10 kDa. The effect of the cross-flow rate, the surfactant to pollutants (S/P) concentration ratio in feed, the variation of pollutants concentration in the feed keeping S/P constant, the presence of Na₂SO₄ and NaCl salts and mixed surfactants on the rejection of each solute and permeate flux have been studied in detail. The % rejection of phenol and o-cresol without using the surfactant observed was 24% and 41% respectively, which was increased to 60% for phenol and 80% for o-cresol at S/P ratio of 8. The effect of salts was also investigated. There was no significant effect of the cross-flow rate on the % rejection of the solutes. The effect of the membrane pore size was also investigated using 1 KDa and 30 KDa PES membranes. Characteristic parameters of MEUF such as the distribution coefficient, micelle loading, and the micelle binding were also estimated.     

Simultaneous recovery of Cr(III) and Cr(VI) from the aqueous phase with ion-exchange membranes

The simultaneous recovery of trivalent and tetravalent chromium ions through charged ion-exchange membranes by using three detachable cells was tested at different current densities. The effect of mono- and divalent valence ions corresponding to trivalent and hexavalent chromium ions in the feed phase was investigated. The recovery factor values of chromium (III) and (VI) ion without current density were obtained and found that it was higher in the absence of binary monovalent and divalent ions, but increased with increasing current density and decreased in the presence of the binary mono- and divalent ions. The transport of both oxidation states of chromium ions through membranes was also correlated with the flux data.     

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.     

胶团强化超滤中SDS临界胶团浓度变化规律研究

用电导法对十二烷基硫酸钠(SDS)的临界胶团浓度(CMC)进行了研究,考虑了温度、pH值、金属离子(Cd2+、Zn2+、Pb2+)浓度变化以及SDS和3种非离子表面活性剂(Brij35、TritonX-100、APG)的复配对溶液CMC值的影响。结果表明,随温度升高,pH值上升,金属离子浓度增加以及Brij35/SDS、TritonX-100/SDS、APG/SDS混合体系配比的增加,溶液CMC值减小。特别当复配比在0.13～1时,CMC值的下降趋势非常明显。这一结果为采用胶团强化超滤技术处理电解锌废水时SDS最佳添加量的确定提供了有效的依据。     

Separation of gold(III) ions from copper(II) and zinc(II) ions using thiourea–formaldehyde or urea–formaldehyde chelating resins

Thiourea–formaldehyde (TF) and urea–formaldehyde (UF) chelating resins were synthesized and these resins were used in the separation of gold(III) ions from copper(II) and zinc(II) base metal ions. In the experimental studies, the effect of acidity on gold(III) uptake and gold(III) adsorption capacities by batch method, and loading and elution profiles of gold(III) ions, gold(III), copper(II), and zinc(II), dynamic adsorption capacities and the stability tests of TF and UF resins by column method were examined. By batch method, the optimum acidities were found as pH 2 and 0.5M HCl, and gold(III) adsorption capacities in the solutions including copper(II) and zinc(II) ions were obtained as 0.088 and 0.151 meq Au(III)/g for UF and TF resins, respectively. On the other hand, by column method, the dynamic adsorption capacities were calculated as 0.109 meq Au(III)/g with TF, 0.023 meq Au(III)/g with UF, 0.015 meq Cu(II)/g with TF, 0.0057 meq Cu(II)/g with UF, and under 6.1 × 10^?5 meq Zn(II)/g with TF or UF. TF resin was more effective in the separation and the concentration of gold(III) ions from copper(II) and zinc(II) ions than UF resin. It was seen that sulfur atoms contributed the gold(III) adsorption comparing with oxygen atoms. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Membrane Characteristics and Fouling Study in MEUF for the Removal of Chromate Anions from Aqueous Streams

Abstract

Micellar‐Enhanced Ultrafiltration (MEUF) of the chromate anions from aqueous solutions has been studied at room temperature (28±2°C) using cationic surfactants, cetyltrimethylammonium bromide (CTAB), and cetylpyridinium chloride (CPC), micelles of which adsorb the chromate ions by electrostatic interactions. The solution is processed by ultrafiltration, using a membrane with a pore size small enough to block the passage of the micelles and the adsorbed ions. The process is highly efficient in removing the chromate ions. In the absence of other electrolytes, chromate ion rejections up to 99% were observed at optimal conditions of pH, pressure, temperature, feed chromate, and surfactant concentrations. The presence of added NaCl reduces the chromate rejection, but it was still considerable (up to 82%), even in the presence of 100 mM NaCl. The rejection rate of chromate was found to be highly dependent on the pH of the feed solution. The influence of membrane characteristics on the chromate ion removal was also studied. Various resistances like fouling resistance, concentration polarization resistance, and membrane resistance were also estimated to quantify their effects on the removal efficiency and on the flux behavior.