Quantitative analysis of chromium(V) by EPR spectroscopy

A procedure to accurately quantitate chromium(V) in environmental and medicinal chemistry samples was developed using electron paramagnetic resonance spectroscopy (EPRS) as the method of detection. It was found to have an error in the order of +/-10% and a detection limit of 0.010 mM (0.5 mg l(-1)) chromium(V). The method has been used to quantitate the formation of chromium(V) in the interaction of chromium(VI) with fulvic acid and a simple model of this acid, viz, 1.2-dihydroxybenzene. Analysis of solutions obtained from the reaction of 1,2-dihydroxybenzene with chromium(VI) demonstrated that even when the organic substrate was present in a 182-fold excess, the maximum chromium(V) concentration attained represented just 1.44% of the initial chromium(VI). Reactions between chromium(VI) and fulvic acid yielded similar results. It was therefore concluded that at background environmental concentrations of chromium and fulvic acid, the production of chromium(V) is insignificant, however, its possible importance in contaminated systems cannot be disregarded on this basis alone. The method for quantitative analysis reported in this paper should be an invaluable tool for investigations into the significance of chromium(V) in the toxicological mechanism of chromium(VI) and its role as a mutagenic agent.     

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.     

Simultaneous determination of arsenic species and chromium(VI) by high-performance liquid chromatography-inductively coupled plasma-mass spectrometry

The simultaneous determination of As(III), As(V), monomethylarsenic acid (MMA), dimethylarsinic acid (DMA) and Cr(VI) in fresh water has been carried out by coupling an anion-exchange column to an inductively coupled plasma-mass spectrometer. Optimisation of chromatographic conditions led to baseline separation of signals from the five species in approximately 9 min using gradient elution. Detection limits were 0.02-0.05 microg As l(-1) and 5.5 microg Cr l(-1). Repeatability was 2-3% for arsenic species and higher, i.e., 8%, for Cr(VI) due to the higher background for this species. Arsenic species and hexavalent chromium stability in surface water samples was evaluated, and storage conditions were set to 1 day at 4 degrees C in polyethylene flasks (without acidification) in order to avoid As(III)-As(V) conversions. The method was applied to the analysis of surface water.     

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.     

Vanadium(III) as an analytical reagent: The titrimetric determination of iron, copper, thallium, molybdenum, uranium, vanadium, chromium and manganese

Vanadium(III) solutions can be used in direct titrations of iron(III), copper(II), thallium(III), molybdenum(VI), uranium(VI), vanadium(V), chromium(VI) and manganese(VII) in milligram amounts. The titrations are done at 70-80 degrees for iron(III), copper(II), thallium(III), molybdenum(VI) and at room temperature for vanadium(V), chromium(VI) and manganese(VII). Uranium(VI) is titrated at 70-80 degrees in presence of iron(II). The vanadium(III) solution is prepared by reduction of vanadium(V) to vanadium(IV) with sulphur dioxide, followed by addition of phosphoric acid and reduction with iodide, and is reasonably stable.     

Simultaneous determination of hexavalent and total chromium in water and plating baths by spectrophotometry

A new spectrophotometric determination method of hexavalent chromium in waste water and plating baths is described based on the oxidation of beryllon III by chromium(VI) in 0.02M sulphuric acid medium. The decrease in the absorbance of beryllon III was measured at 482 nm with an apparent molar absorptivity of 5.15 x 10(4)1.mole(-1).cm(-1). Beer's law was obeyed for chromium(VI) over the range 0-25 mug/25 ml. After the oxidation of Cr(III) to Cr(VI) by ammonium persulphate, total chromium can be determined. Therefore, chromium(III) can be calculated by subtracting chromium(VI) from total chromium. The detection limit is 0.015 and 0.020 mug/25 ml for chromium(VI) and total chromium, respectively. A sensitive spectrophotometric method for trace Cr(III) and Cr(VI) in waste water and plating baths was developed with good precision and accuracy. The reaction is also discussed.     

Determination of vanadium(V) and chromium(VI) in a single sample on a fibrous ion exchanger disk

The determination of vanadium(V) and chromium(VI) in a single sample on a support disk was studied. Polyacrylonitrile fiber filled with an AV-17 anion exchanger was used as a solid phase. After adsorption, the elements were successively detected in the solid phase by color complexation reactions of vanadium with 8-hydroxyquinoline-5-sulfonic acid and chromium with 1.5-diphenylcarbazide. A procedure was developed for the adsorption-spectroscopic determination of 0.04–0.4 μg/mL vanadium(V) and 0.01–0.05 μm/mL chromium(VI) at V: Cr ratios of 1: 1 to 10: 1 in the dynamic mode. The limits of detections for vanadium and chromium were 0.04 and 0.005 μg/mL, respectively. It was shown that the background salt content of potable water had no appreciable effect; no preliminary sample preparation was required.     

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.     

Spectrophotometric study of the complexation and extraction of chromium(VI) with cyanine dyes

Solvent extraction of chromium(VI) ion associates with symmetric cyanine dyes including the heterocyclic radicals of 1,3,3-trimethyl-3N-indoline, benzooxazol, benzothiazol and quinoline has been studied by means of spectrophotometric method. In the acidic medium in the presence of chloride ions, extractable by aromatic hydrocarbons and esters of acetic acids, chromium(VI) ion associates are formed. The molar absorptivities of ion associates are 2.5-3.6x10(5) l mol(-1) cm(-1) in dependence on extractant and dye. The absorbance of the coloured extracts obeys the Beer's law in the range 0.01-2.1 mg l(-1). The extraction of chromium is the highest during extraction from the sulphuric acid medium in the range 0.05-03 M H(2)SO(4). It was found that the Cr(VI):Cl:R molar ratio is 1:1:1. A novel procedure of chromium(VI) extraction and spectrophotometric determination in various types of soils and sewage doped with chromium(VI) was examined.     

Anion-exchange high-performance liquid chromatographic determination of ascorbic acid and hexavalent chromium in rat lung preparations after treatment with sodium chromate in vitro and in vivo

Simultaneous analysis of ascorbic acid and chromium (VI) in soluble fractions and bronchoalveolar lavage fluids of rat lungs treated with sodium chromate in vitro and in vivo was performed by anion-exchange high-performance liquid chromatography coupled to a photodiode-array detector. Absorbances at 265 and 370 nm were used for the determination of ascorbic acid and chromium (VI), respectively. The calibration graphs of standard solutions were linear in the test ranges of ascorbic acid an chromium (VI) (below 10 and 8 ppm, respectively). The detection limits of ascorbic acid and chromium (VI) were 1 and 0.5 ng, respectively. The recovery of ascorbic acid from lung tissues homogenized at pH 7.4 was 99%, and that of chromium (VI) was 96%, when tissues were homogenized under alkaline conditions (pH 11.4). Using this method, ascorbic acid levels in the soluble fractions and lavage fluids of normal rat lungs were determined. In the lung of a rat intratracheally injected with a saline solution of sodium chromate, ascorbic acid decreased to 80% of the normal level, and ca. 90% of the chromium (VI) was reduced within 4 min after injection, indicating that the ascorbic acid-related reduction of chromium (VI) is very rapid. The present method will be useful for studies of the reduction of chromium (VI) by ascorbic acid in biological systems.     

A highly sensitive colour reaction for chromium(VI) with the iodide-basic xanthene dye-pva system

A highly sensitive spectrophotometric method has been developed for determination of chromium(VI), based on oxidation of I(-) to I(-)(3) in acid medium, then formation of a 1:1 ion-association compound of I(-)(3) with a basic xanthene dye in the presence of poly(vinyl alcohol). The molar absorptivity is 1.79 x 10(5) 1.mole(-1).cm(-1) at 600 nm for the Rhodamine B system, 1.56 x 10(5) 1.mole(-1).cm(-1) at 600 nm with Ethylrhodamine B, 1.56 x 10(5) 1.mole(-).cm(-1) at 570 nm with Rhodamine 6G and 2.01 x 10(5) 1.mole(-1).cm(-1) at 590 nm with Butylrhodamine B, respectively. Preconcentration of chromium(VI) by an improved trioctylamine extraction procedure greatly increases the selectivity of the method and can be applied in the spectrophotometric determination of trace amounts of chromium(VI) in tap water, hot-spring water and river water.     

Polarography of metal-gallic complexes

The polarographic behavior of metal ions in perchlorate media containing gallic acid is described. Tungsten(VI) forms a complex with gallic acid which yields a single wave in these media, useful in the polarographic determination of tungsten. Evidence for complexation of chromium(III), copper(II), iron(III), molybdenum(VI), uranium(VI), vanadium(V), tungsten(VI), praseodymium(III), samarium(III), neodymium(III) and gadolinium(III) is obtained and the behavior of these metal ions is summarized.     

New gravimetric method for cobalt

A new gravimetric method for the determination of cobalt is described, based on precipitation from acidic solution with a reagent prepared by heating alpha-nitroso-beta-naphthol in a mixture of glacial acetic acid, hydrogen peroxide and syrupy phosphoric acid. The cobalt is weighed, after ignition of the precipitate, as Co(3)O(4). Iron(III), copper, chromium(III), vanadium(V), tungsten(VI), aluminium, molybdenum, nickel, titanium, zirconium, uranium(VI) and cerium do not interfere.     

Method for the determination of chromium (VI) as chromium (VI)-dibenzyidithiocarbamate

Dibenzyldithiocarbamic acid (DBDC) exhibits the ability to speciate between chromium(VI) and chromium(III), since only the chromium(VI) will form complexes with DBDC. The complex is then extracted into an organic solvent and assayed using an ultraviolet-visible (UV-VIS) spectrophotometer at 498.8 nm. Using 250 ml of aqueous sample detection limits less than 1 ng/ml are possible, while the linear range extends to 500 gmg/ml when working at 498.8 nm. Oxidation of the chromium(III) to chromium (VI) using cerium (IV) enables the determination of total chromium and subsequently the chromium (III) in solution. Evaluation of the method with a standard reference material produced only 4.81 part per thousand error in the determination of chromium(VI).     

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.     

Determination of tributyltin in toluene extract from sea water by graphite furnace atomic absorption spectrometry with a new matrix modifier

A new matrix modifier composed of calcium and chromium[VI] was proposed for the determination of tributyltin (TBT) in toluene extract from sea water containing sediment by graphite furnace atomic absorption spectrometry (GFAAS). Fourteen inorganic and organic compounds (barium, calcium, chromium[VI], lanthanum, magnesium, nickel, palladium, strontium, calcium-chromium[VI], calcium-strontium, nickel isocaprylate, 5%-, 10%-aqueous solution of ascorbic acid and toluene-saturated solution of ascorbic acid) as a matrix modifier were comparatively studied and a matrix modifier composed from 5 microg of calcium and 1 microg of chromium[VI] was found to give the best performance. The interference effects of co-existing elements in sea water containing sediment (aluminium, iron, magnesium, sodium and strontium) were studied. TBT in eight toluene extracts was determined by GFAAS with the proposed matrix modifier. The relative standard deviation was 3.0% for 63 ng ml(-1) of TBT (n = 11). The recoveries were 88-104%. The characteristic mass was 7 pg. The linearity range was 0-250 ng mg(-1).     

Spectrophotometric micro-method for the determination of ethanol in commercial beverages

 A sensitive spectrophotometric method for the determination of ethanol with potassium dichromate was developed. Chromium(VI), in 7 mol L^-1 perchloric acid, reacts quantitatively with ethanol to form chromium(III) and acetic acid. The reaction is complete in about 15 min at room temperature and the chromium(VI) consumed may be determined by the decrease of the absorbance at 267 nm. The analytical working parameters (such as acidity and ionic strength of the solution, temperature and time of the reaction, chromium(VI) concentration, matrix interferences) were optimized. The apparent molar absorptivities of chromium(VI), in the monomer and dimer form, and the equilibrium quotient for the dimerization reaction were determined in 3 mol L^-1 perchloric acid solution. The method was applied to the analysis of micro samples of commercial beverages (beers, wines and spirits) without the previous distillation of ethanol. Received: 9 April 1996/Revised: 3 June 1996/Accepted: 11 June 1996     

Preconcentration of chromium(III) and speciation of chromium by electrothermal atomic absorption spectrometry using cellulose adsorbent

A simple and sensitive method has been developed for species selective determination of chromium(III) and chromium(VI) in water by electrothermal atomic absorption spectrometry. The procedure is based on selective absorption of Cr(III) on a cellulose micro column (pH 11, 0.5 mol L(-1) NaCl). Total chromium was subsequently determined after appropriate reduction of Cr(VI) to Cr(III). Recoveries of more than 97% were found. A concentration factor of 100 was achieved. The relative standard deviations (n=10) at the 40 ng L(-1) level for chromium(III) and chromium(VI) were 2.3% and 1.8% and corresponding limits of detection (based on 36) were 1.8 ng L(-1) and 5.1 ng L(-1), respectively. No interference effects have been observed from other investigated species and the method has been successfully applied to natural water samples.     

快速溶剂萃取-离子色谱法同时测定塑料中的三价铬和六价铬

建立了采用快速溶剂萃取-离子色谱同时测定塑料中三价铬和六价铬的方法。三价铬和六价铬分别以吡啶-2,6-二羧酸(PDCA)和1,5-二苯卡巴肼(DPC)作为络合剂在柱前和柱后进行衍生化,分别在紫外和可见波长下采用紫外检测器进行检测,灵敏度高,基体干扰小。本方法对三价铬和六价铬的检出限分别为5.0 μg/L和0.5 μg/L;分别在50～1000 μg/L和5.0～100 μg/L范围内呈现良好的线性关系,线性相关系数分别为0.9994和0.9998;三价铬和六价铬的回收率范围为90.7%～101.1%,相对标准偏差(RSD)为1.7%～4.4%。该方法分析速度快、灵敏度高、重现性好,可用于塑料中三价铬和六价铬的同时测定。     

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%.