Electroreduction of chromic acid during the chromium deposition: An RRDE study

The rate of the trivalent chromium ion formation during the chromic acid reduction in the presence of sulfate ions is studied in a wide potential range by the RRDE method. At potentials of incomplete reduction of chromate ions, the reaction is attendant by a side process (probably, the hydrogen ion reduction). With a phase film covering the disk cathode, the ring current does not correspond to the number of Cr(III) ions formed at the disk, rather it characterizes the oxidation of products of a phase film comprising oxide-hydroxide compounds of Cr(III). The hypothesis about the formation of a phase cathodic film, presumably preceding the metallic chromium deposition, is confirmed experimentally. The oxide-hydroxide species of Cr(III), which are main film-forming substances, undergo phase transitions in a zone that depends on the sulfate ion concentration. The phase transitions whose products may reach the ring electrode occur in the near-electrode layer. The lower the sulfate ion concentration, the larger the extension of the layer.     

Effect of hydrodynamic electrolysis conditions on the kinetics of cathodic processes in chromium(III) sulfate electrolytes

The effect of stirring on the kinetics of electrode processes in a chromium-plating electrolyte based on chromium(III) sulfate is studied. The electrolyte, in which thick (up to 120 μm) hard chromium coatings can be obtained, is stirred with a magnetic stirrer. Hydrodynamic conditions in the system are calibrated in a modeling solution containing the same components as the electrolyte (with the exception of chromium sulfate which is replaced by an equivalent amount of aluminum sulfate), by the reaction of discharge of hydronium ions. It is shown that reactions of discharge of hydronium ions and incomplete reduction of trivalent chromium ions occur in a diffusion mode. The Cr(III)-Cr(II) system is classified with quasi-reversible redox electrodes and is described by the known equation for diffusion kinetics. The electrodeposition of metallic chromium occurs in the mixed kinetics mode     

水溶液中六价铬在碳纳米管上的吸附

针对用碳纳米管对水溶液中六价铬的吸附净化进行了研究, 考察了溶液浓度、溶液pH值、共存的三价铬离子等因素对吸附行为的影响. 实验结果表明, 碳纳米管在室温下对于六价铬的吸附量随着平衡浓度的增大而升高, 在铬浓度为493.557 mg•L−1时碳纳米管吸附量达到最大值为532.215 mg•g−1; 六价铬的浓度在300~700 mg•L−1的范围内, 碳纳米管对铬的吸附量变化不大；大于700 mg•L−1时, 随着铬的平衡浓度的升高碳纳米管对铬的吸附量降低, 铬浓度为961.074 mg•L−1时, 碳纳米管吸附量降至194.631 mg•g−1. 在pH值为2~7的范围内, 碳纳米管对六价铬的吸附量随着溶液pH值的减小而增大; 而在碱性条件下, pH值对碳纳米管吸附六价铬的影响不大. 溶液中存在三价铬时, 碳纳米管对六价铬的吸附量明显降低, 表明三价铬与六价铬有竞争吸附. 此外, 活性炭的对比吸附实验表明, 在低浓度时, 譬如在六价铬浓度为190 mg•L−1吸附时, 碳纳米管对铬的吸附量约为活性炭的6倍；而在高浓度下, 譬如六价铬浓度为493 mg•L−1时, 碳纳米管对铬的吸附量约为活性炭的2倍.     

Adsorption of chromium from aqueous solution using chitosan beads

A basic investigation on the removal of Cr(III) and Cr(VI) ions from aqueous solution by chitosan beads was conducted in a batch adsorption system. The chitosan beads were prepared by casting an acidic chitosan solution into an alkaline solution. The influence of different experimental parameters; pH, agitation period and different concentration of Cr(III) and Cr(VI) ions was evaluated. A pH 5.0 was found to be an optimum pH for Cr(III) adsorption, and meanwhile pH 3.0 was the optimum pH for the adsorption of Cr(VI) onto chitosan beads. The Langmuir and Freundlich adsorption isotherm models were applied to describe the isotherms and isotherm constants for the adsorption of Cr(III) and Cr(VI) onto chitosan beads. Results indicated that Cr(III) and Cr(VI) uptake could be described by the Langmuir adsorption model. The maximum adsorption capacities of Cr(III) and Cr(VI) ions onto chitosan beads were 30.03 and 76.92 mg g⁻¹, respectively. Results showed that chitosan beads are favourable adsorbents. The Cr(III) and Cr(VI) ions can be removed from the chitosan beads by treatment with an aqueous EDTA solution.     

Electrode processes and their kinetic parameters in the reduction and oxidation of Cr(III) and Cr(II) in molten CsCl

The reduction of chromium ions in the CsCl-CrCl₃ melt in wide concentration and temperature ranges is reported. It is assumed that the melt contains polynuclear chromium complexes. The reduction of Cr(III) to Cr(II) is a reversible one-electron process. The electroreduction of divalent chromium to chromium metal is an irreversible process involving dinuclear and mononuclear chromium complex ions. The electron transfer rate constant has been calculated for various temperatures and chromium chloride concentrations in the salt melt. The activation energy of electron transfer and its dependence on the CrCl₃ concentration in the electrolyte have been determined for the Cr(III) ↔ Cr(II) process.     

Adsorptive stripping voltammetric determination of chromium in gallium

The electroanalytical chemistry of trace metals has progressed strongly with the development of cathodic stripping voltammetry (CSV) preceded by adsorption collection of organic metal complexes. A sensitive method for the determination of trace amount of chromium in gallium is described. Gallium is dissolved in sodium hydroxide containing hydrogen peroxide. The method is based on the catalytic activity of nitrate ions on the reduction of Cr(III)TTHA (triethylene tetramine-N,N,N',N',N',N'-hexaacetic acid) complex. The sensitivity of this method is further improved by adsorption preconcentration of Cr(III)TTHA complex at a hanging mercury drop electrode (HMDE). The Cr(III) formed at the electrode surface by the reduction of Cr(VI), which is present in the bulk solution, is immediately complexed by TTHA. The adsorbed complex is then reduced at a peak potential of - 1.26 V, and the peak height of Cr(III) reduction is measured. The determination limit was restricted by the amount of chromium present in the reagent blank solution. The method is suitable for the determination of chromium at level as low as 0.2 mug g(-1) (with about 50 mg of sample) and a relative standard deviation of 15%.     

Cathodic Reduction of Chromium on a Surface of Nickel Modified by Aromatic Carboxylic Acids

Effect of organic compounds (salicylic, acetylsalicylic, and p-nitrobenzoic acids) adsorbed on a nickel surface or introduced into solution on the cathodic reduction of Cr(VI) is studied by measuring voltammetric curves in a wide potential range up to the beginning of electrodeposition of black chromium. If the adsorbate is salicylic or p-nitrobenzoic acid, only the maximum current corresponding to incomplete reduction Cr(VI) Cr(III) increases in cathodic polarization curve (PC). On a surface modified by acetylsalicylic acid, in addition to an increase in the maximum current, all parts of PC shift towards positive potentials. The Cr(VI) reduction on modified surfaces accelerates presumably due to the electron transfer from the cathode surface onto Cr(VI) atoms, accelerated by the formation of bridges with an increased electron conduction.     

Separation of chromium (III) and chromium (VI) by capillary electrophoresis using 2,6-pyridinedicarboxylic acid as a pre-column complexation agent

A simple method was developed for the simultaneous determination of Cr(III) and Cr(VI) by capillary zone electrophoresis (CZE), where Cr(III) was chelated with ligands to form anionic complexes. Nitrilotriacetic acid, N-2-hydroxyethylenediaminetriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and 2,6-pyridinedicarboxylic acid (PDCA) were investigated as Cr(III) complexing ligands. Of all the ligands studied, 2,6-PDCA with Cr(III) gave the largest UV response and high selectivity for Cr(III). In addition, the condition for pre-column derivatization, including pH, concentration ratio [Cr(III)/2,6-PDCA] and the stability of Cr(III) complexes were also examined. The separation of anionic forms of Cr(III) and Cr(VI) was achieved using co-CZE with UV detection at 185 nm. The electrolyte contained 30 mM phosphate, 0.5 mM tetradecyltrimethylammonium bromide, 0.1 mM 2,6-PDCA and 15% (v/v) acetonitrile at pH 6.4. The detection limits were 2 microM for Cr(III) and 3 microM for Cr(VI) and linear plots were obtained in a concentration range of 5-200 microM. The utility of the method was demonstrated for the determination of Cr(III) and Cr(VI) in contaminated soils.     

Trace Analysis of Iron in Environmental Water and Snow Samples from Poland

Abstract

A voltammetric method for the determination of iron at detection limit of 4 μg/l is described, using the catalytic current of the reduction of the Fe(III)-triethanolamine (TEA) complex in the presence of bromate ions. the determination was performed at a mercury hanging drop electrode without preconcentration, using the TEA alkaline solution as a supporting electrolyte and the differential pulse technique. A peak current for the Fe(III)-TEA catalytic reduction was observed at a potential of-1.0 V (Ag/AgCl saturated electrode). the influence of TEA, BrO³ and NaOH concentrations on the peak height was studied. It was found that a 100-fold excess of Mn, a 50-fold excess of Cr(VI) and Zn did not interfere in the determination. This method was applied to the determination of iron in water, snow and waste water samples.     

Speciation of chromium by in-capillary reaction and capillary electrophoresis with chemiluminescence detection

A sensitive method for the simultaneous determination of chromium(III) (Cr3+) and chromium(VI) (CrO4(2-)) using in-capillary reaction, capillary electrophoresis (CE) separation and chemiluminescence (CL) detection was developed. The chemiluminescence reaction was based on luminol oxidation by hydrogen peroxide in basic aqueous solution catalyzed by Cr3+ ion followed by capillary electrophoresis separation. Based on in-capillary reduction, chromium(VI) can be reduced by acidic sodium hydrogensulfite to form chromium(III) while the sample is running through the capillary. Before the electrophoresis procedure, the sample (Cr3+ and CrO4(2-)), buffer and acidic sodium hydrogensulfite solution segments were injected in that order into the capillary, followed by application of an appropriate running voltage between both ends. As both chromium species have opposite charges, Cr3+ ions migrate to the cathode, while CrO4(2-) ions, moving in the opposite direction toward the anode, react with acidic sodium hydrogensulfite which results in the formation of Cr3+ ions. Because of the migration time difference of both Cr3+ ions, Cr(III) and Cr(VI) could be separated. The running buffer was composed of 0.02 mol l(-1) acetate buffer (pH 4.7) with 1 x 10(-3) mol l(-1) EDTA. Parameters affecting CE-CL separation and detection, such as reductant (sodium hydrogensulfite) concentration, mixing mode of the analytes with CL reagent, CL reaction reagent pH and concentration, were optimized. The limits of detection (LODs) of Cr(III) and Cr(VI) were 6 x 10(-13) and 8 x 10(-12) mol l(-1) (S/N=3), respectively. The mass LODs for Cr(III) and Cr(VI) were 1.2 x 10(-20) mol (12 zmol) and 3.8 x 10(-19) mol (380 zmol), respectively.     

Rapid speciation analysis of Cr(VI) and Cr(III) by reversed-phase high-performance liquid chromatography with UV detection

A simple and rapid method is developed for the simultaneous determination of Cr(VI) and Cr(III) based on the formation of their different complexes with ammonium pyrrolidine-dithiocarbamate (APDC). Separation is performed using reversed-phase high-performance liquid chromatography coupled with UV detection. The conditions for complex formation and speciation are determined, such as solution pH, amount of APDC, temperature, and type of mobile phase. In order to substantially reduce the analysis time, the separation is carried out without extraction of chromium-APDC complexes from the mother liquor. Under the optimum analysis conditions, the chromatograms obtained show good peak separation, and the absolute detection limits (3s) are 2.2 microg/L for Cr(VI) and 4.5 microg/L for Cr(III). The calibration curves are linear from 3 to 5000 microg/L for Cr(VI) and 5 to 3000 microg/L for Cr(III). The relative standard deviations of peak areas in five measurements using a sample solution of 200 microg/L are less than 2% for Cr(VI) and 4% for Cr(III), indicating good reproducibility for this analytical method. Furthermore, simultaneous determination of Cr(VI) and Cr(III) is successful with the application of the proposed procedure in the synthetic wastewaters containing common heavy metal ions: Fe(III), Pb(II), Cd(II), Cu(II), and Zn(II).     

New insights on the mechanism of oxidation of D-galacturonic acid by hypervalent chromium

The pollutant Cr(VI) is known to be very carcinogenic. In conditions of excess of Cr(VI), oxidation of D-galacturonic acid (Galur), the major metabolite of pectin, yields d-galactaric acid (Galar) and Cr(III). The redox reaction takes place through a multistep mechanism involving formation of intermediate Cr(II/IV) and Cr(V) species. The mechanism combines one- and two-electron pathways for the reduction of Cr(IV) by the organic substrate: Cr(VI)→ Cr(IV)→ Cr(II) and Cr(VI)→ Cr(IV)→ Cr(III). This is supported by the observation of the optical absorption spectra of Cr(VI) esters, free radicals, CrO(2)(2+) (superoxoCr(III) ion) and oxo-Cr(V) complexes. Cr(IV) cannot be directly detected; however, formation of CrO(2)(2+) provides indirect evidence for the intermediacy of Cr(II/IV). Cr(IV) reacts with Galur much faster than Cr(V) and Cr(VI) do. The analysis of the reaction kinetics via optical absorption spectroscopy shows that the Cr(IV)-Galur reaction rate inversely depends on [H(+)]. Nevertheless, high [H(+)] still does not facilitate accumulation of Cr(IV) in the Cr(VI)-Galur mixture. Cr(VI) and the intermediate Cr(V) react with Galur at comparable rates; therefore the build-up and decay of Cr(V) accompany the decay of Cr(VI). The complete rate laws for the Cr(VI), Cr(V) and Cr(IV)-Galur redox reaction are here derived in detail. Furthermore, the nature of the five-co-ordinated oxo-Cr(V) bischelate complexes formed in Cr(VI)-Galur mixtures at pH 1-5 is investigated using continuous-wave and pulsed electron paramagnetic resonance (EPR) and density functional theory (DFT).     

Speciation of chromium in water using crosslinked chitosan-bound FeC nanoparticles as solid-phase extractant, and determination by flame atomic absorption spectrometry

Crosslinked chitosan-bound FeC nanoparticles (CCBFeCNP) were prepared, and the adsorptive behavior of Cr(III) and Cr(VI) on CCBFeCNP were assessed. At pH 6.0–10.0, CCBFeCNP is selective towards Cr(III) but hardly selective towards Cr(VI). The retained Cr(III) is subsequently eluted with 0.5 mol L⁻¹ HCl. Total chromium is determined after reduction of Cr(VI) to Cr(III) by ascorbic acid. A new method of flow injection using a micro-column packed with CCBFeCNP as solid phase extractant has been developed for speciation of Cr(III) and Cr(VI) in water samples, followed by flame atomic absorption spectrometry. The effects of pH, sample flow rate and volume, elution solution and interfering ions on the recoveries of Cr(III) were systematically investigated. Under optimum conditions, the adsorption capacity of CCBFeCNP for Cr(III) is 10.5 mg g⁻¹ at pH 7.5. The procedure presented was applied to chromium speciation in water samples, and the results were satisfactory.     

Speciation of Chromium in Natural Waters,Tea, and Soil with Membrane Filtration Flame Atomic Absorption Spectrometry

A sensitive and selective method was developed for the speciation of chromium(III) and chromium(VI) in environmental samples based on membrane filtration and determination by flame atomic absorption spectrometry. Chromium(III) reacts with cochineal red A, yielding a complex that is adsorbed on a cellulose acetate membrane filter, whereas chromium(VI) remains in aqueous solution, permitting separation. After reduction of chromium(VI) to chromium(III) with hydroxylamine hydrochloride, the total concentration of chromium was determined, and the concentration of chromium(VI) was calculated by subtraction. The pH, amount of cochineal red A, and sample volume were optimized on the basis of the recovery of Cr(III). The influence of matrix ions was also investigated. The preconcentration factor was 94. The detection limit (3 sigma) for Cr(III) was 1.4 micrograms per liter. The method was validated using environmental certified reference materials. The method was successfully employed for the speciation of chromium in wastewater and lake water.     

Simultaneous determination of Pt and Rh by catalytic adsorptive stripping voltammetry, using hexamethylene tetramine (HMTA) as complexing agent

Characteristics of the adsorption/electro-reduction of Pt/Rh hexamethylene tetramine (HMTA) complex on static mercury drop electrode surface were studied. Cyclic voltammetry was carried out to get the insight about the mechanistic behaviour of the catalytic current obtained in the voltammetric scan of Pt/Rh HMTA complex in acidic solution. Adsorptive stripping voltammetry using HMTA as the complexing agent was found to be highly sensitive method for the determination of Pt/Rh. Voltammetric measurements were carried out using hanging mercury drop electrode (HMDE) as the working electrode, a glassy carbon rod as the counter and an Ag/AgCl/KCl_saturated as the reference electrode. Various electrochemical parameters like deposition potential, deposition time, concentration of the ligand, supporting electrolyte etc. were optimized. The detection limit of Pt and Rh was found to be 4.38 pML⁻¹ and 2.80 pML⁻¹, respectively for the deposition time of 30 s. Simultaneous determination of Pt(II) and Rh(III) in water samples was possible. The method was found to be free from the commonly occurring interfering ions such as Cu(II), Cd(II), Zn(II), Pb(II), Cr(III), Cr(VI), Fe(III), Fe(II), Ni(II) and Co(II). Spike recovery tests for both Pt and Rh in tap water and sea water samples were also carried out. The method has been verified by analyzing certified reference material (WMG-1).     

Extraction of metal ions with a primary amine

This paper describes some experimental results obtained at the extraction of sulfate solutions of U(VI), Mo(VI), V(V), Ce(IV), Zr(IV), Fe(III), Al(III) with a benzene solution of Primene JMT. The aqueous solutions consist of metal sulfates (or other metal salts) in the presence of sulfuric acid with a concentration range of 0–2.1 mol·dm^–3, the concentration of amine in the organic phase being 0.1–0.3 mol·dm^–3. The presence of various species of metal ions in the aqueous phase is considered and the equilibrium concentration of substances extracted in the organic phase is determined. On the basis of the results of chemical analysis (concentration of metals and sulfate ions) the composition of the prevailing complexes in the organic phase is proposed.     

Sonoassisted Microbial Reduction of Chromium

This study presents sonoassisted microbial reduction of hexavalent chromium (Cr(VI)) using Bacillus sp. isolated from tannery effluent contaminated site. The experiments were carried out with free cells in the presence and absence of ultrasound. The optimum pH and temperature for the reduction of Cr(VI) by Bacillus sp. were found to be 7.0 and 37 °C, respectively. The Cr(VI) reduction was significantly influenced by the electron donors and among the various electron donors studied, glucose offered maximum reduction. The ultrasound-irradiated reduction of Cr(VI) with Bacillus sp. showed efficient Cr(VI) reduction. The percent reduction was found to increase with an increase in biomass concentration and decrease with an increase in initial concentration. The changes in the functional groups of Bacillus sp., before and after chromium reduction were observed with FTIR spectra. Microbial growth was described with Monod and Andrews model and best fit was observed with Andrews model.     

Study of chromium(VI) adsorption onto modified activated carbons with respect to analytical application

Two different types of modification of activated carbon, by treatment with concentrated solution of HNO₃ and outgassing treatment at high temperature, were studied in order to obtain the most effective adsorption of chromium(VI) ions from water solution. The basic parameters affecting the adsorption capacity of Cr(VI) ions on modified activated carbons were studied in details and the effect of modifications of activated carbons has been determined by studying the initial runs of adsorption isotherms. The obtained Cr(VI) adsorption isotherms were well fitted in the Freundlich equation. The reduction of Cr(VI) to Cr(III) and further ion exchange mechanism of adsorption onto oxidizing activated carbon and surface precipitation to Cr(OH)₃ in case of outgassing activated carbon were found as the main adsorption mechanisms of Cr(VI) ions onto modified activated carbons. Presence of chlorides and nitrates in studied adsorption system strongly decreased the adsorption ability of Cr(VI) onto outgassing activated carbon and mechanism of this behavior is proposed.     

Speciation of chromium (III) and chromium (VI) by capillary electrophoresis with contactless conductometric detection and dual opposite end injection

A sensitive, rapid and inexpensive capillary electrophoretic method for the determination of Cr(III) and Cr(VI) species is presented. The method is based on the dual opposite end injection principle and contactless conductometric detection. The sample containing cationic and anionic species is injected into the opposite ends of the separation capillary and after the high voltage is applied, the analytes migrate towards the capillary center, where the cell of a contactless conductivity detector is placed. The method does not require any sample pretreatment, except dilution with deionized water. The separation of Cr(III), Cr(VI) and other common inorganic anions and cations is achieved in less than 4 min. The parameters of the separation electrolyte solution, such as pH and concentration of L-histidine, were optimized. Best results were achieved with electrolyte solution consisting of 4.5 mM L-histidine, adjusted to pH 3.40 with acetic acid. The detection limits achieved for Cr(III) and Cr(VI) were 10 and 39 microg.L(-1), respectively. The repeatability of migration times and peak areas was better than 0.3% and 2.8%, respectively. The developed method was applied to the analyses of rinse water samples from the galvanic industry. The results for the determination of Cr(III) and Cr(VI) were in good agreement with the results obtained by certified differential spectrophotometric method using diphenylcarbazide (CN 83 0520-40) and with the results for the total chromium concentrations determined by electrothermal atomic absorbance spectrometry (ET-AAS) and inductively coupled plasma-mass spectrometry (ICP-MS).     

Optimization of Parameters for Cr(VI) Adsorption on Used Black Tea Leaves

Dynamic characteristics of Cr(VI) sorption on used black tea leaves (UBTLs) as a low-cost adsorbent are studied. Batch experiments were conducted to evaluate the effects of Cr(VI) concentration, solution pH and temperature on the removal process. Both of adsorption and reduction, involved in the process, are affected by the processing parameters. The adsorption kinetics is described successfully using pseudo-second order rate equation and the rate constant decreases with increasing the initial concentration of Cr(VI) up to 150 mg/L (for 0.1 g/L UBTLs) then becomes slow. Experimental and calculated kinetic data for equilibrium are well expressed by Langmuir isotherm. The solution pH has a profound effect on the adsorption rate. The rate constant increases linearly with an increase in temperature, and the low value of activation energy of adsorption, 16.3 kJ/mol, indicates that Cr(VI) is easily adsorbed on UBTLs. The maximum Cr(VI) adsorptive conditions, with a minimum reduction, were achieved from the dynamics of operational parameters: the initial Cr(VI) concentration < 150 mg/L (for 0.1 g/L UBTLs); the initial solution pH = 1.54–2.00 and the processing temperature < 50 ^∘C, for the possibility of its practical application.