Colour reaction of chromium (VI) with N,N-diethyl-1,4-phenylenediame in the presence of ethanol and cyclohexyldiamine tetraacetic acid as well as its application in the species analysis of chromium

A simple, rapid and precise spectrophotometric method for the determination of Chromium (III and IV) has been developed. The reaction of Cr(VI) with N,N-diethyl-1,4-phenylenediamine is almost complete in a twinkling, which yields a red product with a wavelength of maximum absorption at 530 nm. Beer's Law is obeyed in the Cr concentration range of 0-2.0 mug ml(-1). The molar absorptivity is 5.0x10(4) l mol(-1) cm(-1), limit of detection 0.002 mug ml(-1) and relative SD=1.13% for 5.04 mug Cr. The colouring rate and absorbance are not noticeably affected by temperature from 2 to 45 degrees C. The amounts of Cr(VI) and Cr(III) were measured by determining Cr(VI) first under the condition of masking Cr(III) by cyclohexyldiamine tetraacetic acid, and then the total amount by oxidation of Cr(III). The method was applied to the analyses of some industrial waste waters containing Cr with satisfactory results.     

Speciation of Cr(III) and Cr(VI) by Means of Melamine-Urea-Formaldehyde Resin and FAAS

 A method is described for the quantitative preconcentration and separation of trace chromium in water by adsorption on melamine-urea-formaldehyde resin. Cr(VI) is enriched from aqueous solutions on the resin. After elution the Cr(VI) is determined by FAAS. The capacity of the resin is maximal at ∼ pH 2. Total chromium can be determined by the method after oxidation of Cr(III) to Cr(VI) by hydrogen peroxide. The relative standard deviations (10 replicate analyses) for 10 mg/L levels of Cr(VI), Cr(III) and total chromium were 1.5, 3.5 and 2.8% respectively. The procedure has been applied to the determination and speciation of chromium in lake water, tap water and chromium-plating baths.     

Rapid determination of chromium(VI) in electroplating waste water by use of a spectrophotometric flow injection system

A new rapid and sensitive FI method is reported for spectrophotometric determination of trace chromium(VI) in electroplating waste water. The method is based on the reaction of Cr(VI) with sodium diphenylamine sulfonate (DPH) in acidic medium to form a purple complex (lambda(max) = 550 nm). Under the optimized conditions, the calibration curve is linear in the range 0.04-3.8 microg ml(-1) at a sampling rate of 30 h(-1). The detection limit of the method is 0.0217 microg ml(-1), and the relative standard deviation is 1.1% for eight determinations of 2 microg ml(-1) Cr(VI). The proposed method was applied to the determination of chromium in electroplating waste water with satisfactory results.     

Ion-pair chromatographic determination of chromium(VI)

Ion-pair chromatography (IPC) with conductometric detection was investigated as a precise and selective analytical method for the determination of chromium in electro-plating solutions and waste waters. Chromatographic parameters were optimized for separation of Cr(VI) and SO(2-)(4). The analytical column (100 x 6 mm) was packed with 10 mum silasorb C(18) (Czechoslovakia). Tetrabutylammonium butyrate (TBAB), at pH 7.0 in acetonitrile-water (18:82 v/v) mixture, was used as the eluent. Two samples of solution are taken for the analysis. In the first of them the amount of Cr(VI) is determined, in the second one Cr(III) is oxidized to Cr(VI) with H(2)O(2) in alkaline medium and the total amount of Cr is determined. From the difference of the two obtained results the concentration of Cr(III) is calculated. The detection limit of Cr(VI) is 0.1 mug/ml and the relative standard deviation (at the 1.0 mug/ml) is 4.0%. The IPC results for chromium agreed closely with these obtained by spectrophotometry.     

Chromium speciation by a surfactant-coated alumina microcolumn using electrothermal atomic absorption spectrometry

A simple and convenient method has been developed for the speciation of chromium(III) and chromium(VI) in aqueous solutions using a sodium dodecyl sulphate coated alumina micro-column (1.5 cm x 5 mm i.d.) and graphite furnace-atomic absorption spectrometry (GF-AAS). Under the optimized conditions (pH 0.6, adjusted with hydrochloric acid; flow rate, 1 ml min(-1)) chromium(VI) is retained on the column and chromium(III) is collected and determined by GF-AAS. Total chromium is directly determined by GF-AAS and chromium(VI) is calculated by difference. The relative standard deviations (10 replicate analyses) at the 20 mug l(-1) level for chromium(III) and chromium(VI) and at the 40 mug l(-1) level for total chromium were 1.4%, 3.6% and 1.8%, and the corresponding limits of detection (based on 3sigma) were 0.57 mug ml(-1), 0.61 mug ml(-1) and 0.35 mug l(-1) respectively. No large interference effects have been observed from other investigated species and the method has been successfully applied to a range of water samples.     

Sequential injection wetting film extraction applied to the spectrophotometric determination of chromium(VI) and chromium(III) in water

The spectrophotometric determination of Cr(VI) and Cr(III) via sequential injection was used to demonstrate the sensitivity enhancement provided by a newly developed wetting film extraction system. The reaction product of Cr(VI) with 1,5-diphenylcarbazide was ion-paired with perchlorate and extracted into an organic wetting film consisting of octanol and 4-methyl-2-pentanone on the inner wall of a Teflon tube. The wetting film, with the extracted analyte, was then eluted with 100 mul acetonitrile and the analyte determined spectrophotometrically at 546 nm. Important optimized parameters were the selection of wetting film and elution solvents, the flow rate, the length and diameter of the extraction coil and the conditions for the formation of the ion paired chelate. Cr(III) was previously oxidized to Cr(VI) and calculated as the difference between total Cr and Cr(VI). An enrichment factor of 25 and a detection limit of 2.0 mug l(-1) Cr(VI) were achieved with a sampling frequency of 17 h(-1). The calibration curve was linear up to 100 mug l(-1) Cr(VI) (r = 0.999). The relative standard deviations were 2.8 and 2.0% at the 25 and 100 mug l(-1) levels.     

Speciation of Cr(III) and Cr(VI) in water after preconcentration of its 1,5-diphenylcarbazone complex on amberlite XAD-16 resin and determination by FAAS

A simple and sensitive method for the speciation, separation and preconcentration of Cr(VI) and Cr(III) in tap water was developed. Cr(VI) has been separated from Cr(III) and preconcentrated as its 1,5-diphenylcarbazone complex by using a column containing Amberlite XAD-16 resin and determined by FAAS. Total chromium has also been determined by FAAS after conversion of Cr(III) to Cr(VI) by oxidation with KMnO₄. Then, Cr(III) has been calculated by subtracting Cr(VI) from the total. The effect of acidity, amount of adsorbent, eluent type and flow rate of the sample solution on to the preconcentration procedure has been investigated. The retained Cr(VI) complex was eluated with 10 ml of 0.05 mol l⁻¹ H₂SO₄ solution in methanol. The recovery of Cr(VI) was 99.7±0.7 at 95% confidence level. The highest preconcentration factor was 25 for a 250 ml sample volume. The detection limit of Cr(VI) was found as 45 μg l⁻¹. The adsorption capacity of the resin was found as 0.4 mg g⁻¹ for Cr (VI). The effect of interfering ions has also been studied. The proposed method was applied to tap water samples and chromium species have been determined with the relative error <3%.     

Enhanced spectrophotometric determination of chromium (VI) with diphenylcarbazide using internal standard and derivative spectrophotometry

In the present work, erioglaucine A was applied as internal standard to enhanced spectrophotometric determination of chromium (VI) with diphenylcarbazide. The following procedure was used: (1) addition of internal standard and formation of ion pairs of Cr (VI) with benzyltributylammonium bromide (BTAB) (sample volume 100 ml), (2) extraction to 10 ml of methylene chloride, (3) evaporation in nitrogen stream, and (4) redissolution in a micro-volume with addition of diphenylcarbazide for color development (final volume 200 mul). The preconcentration factor achieved was about 400 and it was shown that, using internal standard, the analytical errors due to sample treatment were reduced. The analytical signals for chromium and internal standard were obtained at 591.30 and 653.50 nm from first derivative spectra, normalized against (1)D(653.50nm). The analytical characteristics evaluated were: detection limit = 0.06 mug l(-1), quantification limit = 0.19 mug l(-1), precision for 1 mug l(-1) 14.2%, and for 10 mug l(-1) 3.2%, correlation coefficient of linear regression was 0.9985. The proposed procedure was applied to determination of chromium (VI) in tap water. Total chromium was determined by electrothermal atomic absorption spectrometry, the recovery of hexavalent chromium added was then evaluated and compared with the results of the proposed procedure. In this experiment, good agreement was obtained between results obtained by the two methods.     

Sequential injection analysis for Cr(VI) and Cr(III) with renewable surface reflection spectrophotometry.

On the basis of the chromogenic reaction of chromium(VI) with 1,5-diphenylcarbohydrazide (DPC) on the surface of Polysorb C-18 beads and the sequential injection renewable surface technique (SI-RST), a highly sensitive reflect spectrophotometric method for the determination of chromium(III) and chromium(VI) was proposed. Considerations of system and flow cell design, and factors that influence the determination performance were discussed. With 300 microl of sample loaded and 0.6 mg of beads trapped, the linear response range was 0.02 - 0.5 mg l(-1) Cr(VI) with a detection limit (3 sigma) of 2.4 microg l(-1) Cr(VI). The method achieves a precision of 1.3% RSD (n = 11) and a throughput of 53 samples per hour. The determination of Cr(III) was based on the same reaction for the determination of Cr(VI) after being oxidized by (NH4)2S2O8. The precision of the oxidation method was evaluated using a 0.2 mg l(-1) Cr(III) standard, yielding an RSD of 2.5% (n = 11). The average recovery of Cr(III) oxidized was tested to be 99.1%. The proposed method was used in the simultaneous determination of Cr(VI) and Cr(III) in water samples, and the error was less than 3%.     

Separation of Cr(III) and Cr(VI) using melamine-formaldehyde resin and determination of both species in water by FAAS

A method is described for the determination of Cr(VI) and total chromium by FAAS. Cr(VI) is separated from Cr(III) by adsorption on melamine-formaldehyde resin. After elution of Cr(VI) with 0.1 mol/l NaAc solution, it is analysed by FAAS. Total chromium is determined by FAAS after conversion of Cr(III) to Cr(VI) by oxidation with hydrogen peroxide, total Cr(VI) is concentrated as above. If the total concentration of chromium is sufficient, the determination can be directly made by FAAS. Cr(III) can then be calculated by subtracting Cr(VI) from the total Cr. This method was successfully applied to the determination of chromium in lake water.     

The simple and rapid spectrophotometric determination of trace chromium(VI) after preconcentration as its colored complex on chitin

Preconcentration method with collection of metal complexes on a chitin has been applied to the spectrophotometric determination of chromium(VI) in water. The chromium(VI) is collected as its 1,5-diphenylcarbazide(DPC) complex on a column of chitin in the presence of dodecyl sulfate as counter-ion. The Cr-DPC complex retained on the chitin is eluted with a methanol-1 M acetic acid mixture (7:3, v/v), and the absorbance of the eluent is measured at 541 nm. Beer's law is obeyed over the concentration range of 0.05-0.6 mug of chromium(VI) in 1 ml of the eluent. The apparent molar absorptivity is 3.5x10(4) dm(3) mol(-1) cm(-1). The tolerance limits for Fe(III) is low, i.e. ten times that of chromium(VI), but some metal ions and common inorganic anions do not interfere in concentration range of 100-10 000 times that of chromium(VI). The present method can be applied to the determination of chromium(VI) in natural water samples.     

Spectrophotometric determination of chromium(III, VI) by use of chromium(III, VI)-Chrome AzurolS-cetylpyridinium bromide-hydroxylamine hydrochloride-zinc(II) system

This paper shows that the sensitivity of the Cr(III, VI)—Chrome Azurol S (CAS)-cetylpyridinium bromide (CPB)—hydroxylamine hydrochloride system can be increased and the wavelength of maximum absorption slightly shifted by addition of zinc(II) and that the analytical data are practically identical for both Cr(III) and Cr(VI), indicating that under the conditions used both initial oxidation states of chromium yield the same final oxidation state, Cr(III). On the basis of the Cr(III, VI)—CAS—CPB—NH₂OH·HCl—Zn systems a new, highly sensitive and selective method for spectrophotometric determination of microamounts of Cr(III, VI) has been developed, with molar absorptivity of 1.27 × 10⁵ 1. mole⁻¹ . cm⁻¹ for the complex at 620 nm and linear calibration up to 0.4 μg/ml chromium. Various foreign ions do not interfere. The method can be applied to direct determination of chromium in steels.     

Preconcentration and speciation of chromium using a melamine based polymeric sequestering succinic acid resin: its application for Cr(VI) and Cr(III) determination in wastewater

A new melamine based polymeric sequestering resin was prepared for preconcentration and separation of hexavalent chromium from water, and its sequestering action was investigated. The water-insoluble, cross-linked sequestering resin was formed by reaction with bromosuccinic acid and cross-linking of melamine. The active sequestering group on the resin is NH-(Succinic acid) or salt thereof. The resulting chelating resin was characterized by infrared spectra. The newly prepared resin quantitatively retained Cr(VI) at pH 2.0-4.0 when the flow rate was maintained between 1 and 5 ml min⁻¹. The retained Cr(VI) was instantaneously eluted with 25 ml of 0.1 M NaOH. The chromium species were determined by a flame atomic absorption spectrometer. The limits of detection for Cr(VI) and Cr(III) were found to be 5.3 and 4.2 μg l⁻¹, respectively. The precision and accuracy of the proposed procedure was checked by the use synthetic and reference steel samples. The established preconcentration method was successfully applied to the determination and selective separation of Cr(VI) in electroplating industry wastewater. Total concentrations determined by the spectrophotometric method (110.3±0.6 g l⁻¹ Cr(VI) and 1.2±0.3 g l⁻¹ Cr(III)) are compared with those found by FAAS and the obtained results (110.4±1.8 g l⁻¹ Cr(VI) and 1.4±0.5 g l⁻¹ Cr(III)) show good agreement.     

Malachite green as a reagent for detection and spectrophotometric determination of chromium(VI)

A sensitive and inexpensive method of spectrophotometric determination of chromium(VI), based on the absorbance of its complex with malachite green and acetic acid at pH 2.5 is reported. The complex shows a molar absorptivity of 8 x 10(4) l.mole(-1) cm(-1) at 560 nm, using malachite green and acetic acid as reference solution. The effect of time, temperature, pH and reagent concentration is studied and optimum operating conditions are established. Beer's law is applicable in the concentration range 2.0-22.8 mug/ml chromium(VI). The resin beads act as a catalyst and as little as 1.6 mug of chromium(VI) is detected in the resin phase as compared to 4.1 mug in the solution phase. The standard deviation in the determinations is +/-0.40 mug/ml for a 10.35 mug/ml solution.     

Determination of trace metals and speciation of chromium ions in atmospheric precipitation by ICP-AES and GFAAS

Sampling and analytical techniques used for determining trace metal concentrations in atmospheric precipitation waters collected in Hungary are presented. The results of the analyses are briefly discussed and special attention is devoted to chromium speciation. For the preconcentration of the trace metals a chelating cellulose, iminodiacetic acid ethylcellulose (IDAEC) microcolumn was used in a flow-injected system. Cd, Co, Cu, Fe, Mn, Ni, Pb, Ti, V and Zn were determined by ICP-AES. In precipitation water the concentrations of the trace elements were in the 0.1-50 mug/l. range. The two forms of chromium, Cr(III) and Cr(VI) were separated using IDAEC and the anion exchanger diethylamine ethylcellulose, respectively. Cr was determined by GFAAS. In atmospheric precipitation the concentration of Cr(III) was in the range of 0.1-0.4 mug/l. while that of Cr(VI) in the range of 0.04-0.1 mug/l.     

Determination of chromium in waste-water and cast iron samples by fluorescence quenching of rhodamine 6G

A new simple, selective and sensitive fluorescence quenching method was developed to determine chromium with rhodamine 6G. The method is based on the oxidation of rhodamine 6G by chromium(VI) in sulfuric acid solution. The linear calibration graph was obtained in the range 8-80 ng ml(-1) chromium(VI). The detection limit is 0.8 ng ml(-1). The method was applied successfully to the determination of chromium in waste water and cast iron samples.     

Preconcentration and speciation of chromium in waters using solid-phase extraction and atomic absorption spectrometry

A method for the preconcentration and speciation of chromium was developed. After formation of an anionic compound with ethylenediaminetetraacetic acid (CrY(-)), Cr (VI) and Cr (III) are retained on a strong anionic phase (SAX) and controlled elution with 0.5 M NaCl permits their speciation. The retention and elution conditions were optimised, and interferences due to the presence of other ions such as Mg(II), Mn(II), Sn(II), Fe(III), Ba(II), Al(III), Ca(II), chloride, iodine, bromide, fluoride, sulphate, phosphate, bicarbonate and nitrate were studied. The detection limits were 0.4 mug l(-1) and 1.1 mug l(-1) for Cr(III) and Cr(VI), respectively, and reproducibility was 9%. The results obtained for speciation of chromium by the proposed method in wastewaters are in agreement with the values obtained by a reference method for a 95% confidence level.     

Speciation of chromium (VI) and total chromium determination in welding dust samples by flow-injection analysis coupled to atomic absorption spectrometry

We have studied the speciation of chromium (VI) in stainless-steel welding dusts. The approach used for the analysis of Cr(VI) and total Cr relies on a flow-injection analyzer (FIA) equipped with two different sequential detectors. The system measures Cr(VI). by colorimetry (with 1,5-diphenyl carbohydrazide) and total chromium content by flame atomic absorption spectroscopy (AAS). The extraction of the samples of welding-fume dusts is achieved in a buffer solution (acetic acid and sodium acetate at pH 4). This extraction procedure gives a 96% recovery of chromium (VI). The FIA-AAS system that has been described is also more sensitive, has a lower detection limit (0.005 mug ml(-1)) and gives a better precision (< 1%) than other equivalent systems that have been previously described.     

On the spectrophotometric flow injection determination of chromium(VI) in natural waters after on-line preconcentration on activated alumina

The feasibility of chromium(VI) preconcentration on to activated alumina in a continuous flow system with spectrophotometric detection was investigated. Chemical and flow variables, and the influence of concomitant species were studied both with and without preconcentration systems. The best results were obtained by using a 2.5 cm long, 1.6 mm i.d. alumina minicolumn, and selecting 1 x 10(-4) M nitric acid as the preconcentrating medium and 0.1 M ammonium hydroxide as the eluent. The eluted chromium(VI) was mixed with diphenylcarbazide in acidic medium and the absorbance of the colored complex was measured at 540 nm. Linear calibrations for 5, 25 and 50 ml sample volumes were established over the concentration ranges 10-50 mug 1(-1), 2-10 mug 1(-1) and 1-5 mug 1(-1) with sensitivity enhancements of 44, 196 and 392 and detection limits (3sigma) of 3.0 mug 1(-1), 0.3 mug 1(-1) and 0.2 mug 1(-1), respectively. The methods is relatively fast and cheap. Natural waters were analyzed with use of the developed procedure.     

Studies and application of catalytic kinetic spectrophotometric determination of trace chromium(VI) sensitized by microemulsion medium

A new catalytic kinetic spectrophotometric method for the determination of trace amount of chromium (VI) in microemulsion medium has been developed. The method is based on the catalytic effect of chromium (VI) on the oxidation of nuclear fast red in the presence of Tween-80 microemulsion and HAc-NaAc buffer solution (pH = 5.2). The linear ranges are in the range of 0 approximately 0.0480 microg mL(-1) of Cr (VI) at 528 nm and the detection limit is 1.56x10(-9)g mL(-1). The method has been applied in determination of Cr (VI) in water and food samples with satisfactory results. The relative standard deviation is less than 4.6 % and the recovery is 93.5 approximately 104 %.