The atomic absorption spectroscopy of chromium

Conditions were studied for the determination of trace amounts of chromium by atomic absorption spectroscopy. Solution matrix, flame composition, and extraction procedures were the variables studied. A detection limit of 0.006 p.p.m. of chromium was observed with an air-hydrogen flame and methyl isobutyl ketone as the solvent.     

Studies on the extraction of chromium(VI) by ketones

A study of the extraction of chromium(VI) from aqueous media by ketones was made. Extraction of chromium was found to be most efficient from aqueous hydrochloric acid solutions. A mechanism for the extraction of chromium(VI) from aqueous hydrochloric acid solutions by methyl isobutyl ketone is proposed involving the formation of a receptor in the organic phase, the exchange of the chloride ion of the receptor for the anionic chromium(VI) species of the aqueous phase, and the solvation of the extracted chromium species. The differences in the abilities of various ketones to extract chromium(VI) from aqueous hydrochloric acid solutions, and the differences in the extraction of chromium (VI) from various aqueous acids by methyl isobutyl ketone are attributed to the differences in the formation of receptors.     

Separation of Cr(III) and Cr(VI) using complexation of Cr(III) with 8-hydroxyquinoline and determination of both species in waters by ETA-AAS

Summary A method for the determination of chromium(III) and (VI) species has been studied and applied to mineral water samples. The chromium(III) was chelated with 0.1 mol/l 8-hydroxyquinoline in methyl alcohol, extracted in isobutyl methyl ketone and determined by ETA-AAS. The effects of the pH, extraction and heating time and amounts of the reagents required for the extraction were studied. A method for the determination of total chromium was optimized too, and the chromium(VI) can be calculated. The precision, sensibility, accuracy, graphite furnace program and interferences for both methods were also investigated.     

Hydrodimerisation electrochimique de cetones aromatiques encombrees en milieu aprotique et en presence de chlorure de chrome

The electrochemical reduction of hindered aromatic ketones which are difficult to reduce alone, can be achieved in an aprotic medium (DMF) on a mercury pool cathode, in presence of Cr(III) chloride, at the reduction potential or the Cr(II)/Cr(0) system, but at a less negative potential than that of the ketone itself. There is selective hydrodimerisation into an α-glycol, with total lack of polymerisation. With dissymetric ketones, the dl-diastereoisomers of the diols are produced. The effect of chromium is due either to the reduction of a Cr-ketone complex or to the reduction of the ketone by a film of colloidal chromium on the electrode surface.     

Mechanism of the selective formation of cyclohexanone in the decomposition of cyclohexyl hydroperoxide by chromium stearate

From a comparison of the rates of formation of cyclohexanone and 2-decanone in cyclohexane solutions of cyclohexyl hydroperoxide or tert-butyl-hydroperoxide in the presence of chromium(III) stearate and a mixture of cyclohexanol and 2-decanol in an atmosphere of argon at 350 K, it is concluded that the direct breakdown of cyclohexyl hydroperoxide by chromium stearate leads to selective formation of cyclohexanone. The contribution of the oxidation of cyclohexanol to ketone formation at a cyclohexanol concentration comparable with the hydroperoxide concentration (0.1 M) is 10%.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2239–2242, October, 1991.     

Determination of traces of chromium(vi) as a thiosemi-carbazide complex by solvent extraction and atomic absorption spectrometry

Extraction of chromium(VI) at pH 2—12 with thiosemicarbazide into methyl isobutyl ketone is described. The detection limit is 30 ng ml^-1, and the concentration which gives 1% absorbance is 60 ng ml^-1, when the organic phase is used directly.     

Cr(III)/Cr(VI) speciation in aerosol particles by extractive separation and thermal ionization isotope dilution mass spectrometry

 An isotope dilution mass spectrometric (IDMS) method, using the formation of positive thermal ions, was developed for Cr(III) and Cr(VI) speciation in aerosol particles. Cr(III) and Cr(VI) spike species, enriched in ⁵³Cr, were applied for the isotope dilution step. After leaching of filter collected aerosol samples by an alkaline solution at pH 13, species separation was carried out by extraction with a liquid anion exchanger in methyl isobutyl ketone. Cr(VI) in the organic phase was re-extracted into an ammoniacal solution and chromium was then isolated from both fractions of species by electrodeposition. Detection limits of 30 pg/m³ for Cr(III) and of 8 pg/m³ for Cr(VI) were achieved in atmospheric aerosols for volumes of air samples of about 120 m³. These low detection limits allowed the determination of chromium species in continental aerosol particles in dependence on different seasons. The Cr(III) /Cr(VI) ratio was always found to be about 0.3 whereas dust from soil erosion, which is probably the primary source of chromium in the atmosphere, showed higher ratios. This indicates that chromium is oxidized in the atmosphere. The accuracy of the method was demonstrated in two interlaboratory comparisons of Cr(VI) determinations in welding dust samples. The IDMS method also contributed to the certification of a corresponding standard reference material organized by the Standard Reference Bureau of the European Union. Chromium speciation, including the determination of elemental chromium Cr(0), was carried out in aerosols of different welding processes for stainless steel. These analyses showed distinct differences in the distribution of chromium species in the welding process and can be used as an exact calibration method for routine methods in this important field of monitoring corresponding working places. Received: 19 August 1996/Revised: 24 September 1996/Accepted: 28 September 1996     

Determination of chromium by atomic absorption spectrophotometry of chromium acetylacetonate : Determination of chromium in sea water

A sensitive atomic absorption method is described for the determination of chromium at sub-microgram levels. Chromium(III) is converted to its acetylacetone complex and extracted into MIBK. The atomic absorption sensitivity is thus en hanced two-fold compared to chromium (III) in aqueous medium. The detection limit of chromium is 0.015 p.p.m. with an acetylene-air flame; the sensitivity obtained with other chromium, methods under the same instrumental conditions is compared. The method can be applied to the determination of chromium in sea water; at a level of ca. 1.6 μg Cr/1, the precision is ±0.06 μg/1.     

Diastereoselective synthesis of five- and seven-membered rings by [2+2+1], [3+2], [3+2+2], and [4+3] carbocyclization reactions of beta-substituted (alkenyl)(methoxy)carbene complexes with methyl ketone lithium enolates

beta-Substituted alkenylcarbene complexes react with methyl ketone lithium enolates to give different carbocyclization products depending on the structure of the lithium enolate, on the metal of the carbene complex, and on the reaction media. Thus, the reactions of aryl and alkyl methyl ketone lithium enolates with beta-substituted alkenyl chromium and tungsten carbene complexes in diethyl ether afford 1,3-cyclopentanediol derivatives derived from a formal [2+2+1] carbocyclization reaction. However, the lithium enolates of acetone and tungsten complexes furnish formal [3+2+2] carbocyclization products. In the case of alkynyl methyl ketone lithium enolates, competitive formal [2+2+1] and [3+2] carbocyclization reactions occur and 1,3-cyclopentanediol and 3-cyclopentenol derivatives are formed. Conversely, alkenyl methyl ketone lithium enolates react with alkenylcarbene complexes under the same reaction conditions to form 2-cycloheptenone derivatives by a formal [4+3] carbocyclization reaction. Finally, when the reaction was performed in the presence of a coordinating medium, the [3+2] carbocyclization pattern was observed independently of the nature of the methyl ketone lithium enolate used.     

Determination of copper in saline waters by atomic absorption spectrohotometry combined with apdc-mibk extraction

A technique has been developed for the determination of copper in saline waters by extraction of its complex with ammonium pyrollidine dithiocarbamate into methyl isobutyl ketone and subsequent analysis by atomic absorption spectrophotometry. The method is self-compensating for any incomplete extraction of copper. With a 15:510 solvent-aqueous phase ratio, a sensitivity of 0.2 p.p.b. and a precision of ±10% were achieved. The method was used to determine copper in a number of sea water and other'saline water samples.     

Determination of riboflavin in pharmaceutical products by automatic discrete-sample analysis

A procedure for the determination of iron, copper, nickel, cobalt, manganese and chromium down to 0.01 μg g^-1 in sodium calcium silicate glass, sodium borosilicate glass, sodium carbonate and calcium carbonate is described. The analytical procedure depends on the separation at pH 6 of the metal diethyldithiocarbamates into isobutyl methyl ketone, and their determination by flameless atomic absorption spectrometry, with a Massmann-type graphite furnace. The limiting factors on the detection limits attainable are discussed and related to the purity of the acids used for sample solution, sample contamination during chemical separation and the sensitivity of the analytical technique.     

Investigation of chromium(III) acetylacetonate as a calibration reference material for atomic absorption spectroscopy

It is shown that chromium(III) acetylacetonate meets the requirements of calibration reference materials: it is homogeneous, soluble in water and organic solvents, and its solutions are stable. Chromium(III) acetylacetonate has been successfully used as a calibration reference material in the analysis of chromium in iron-base alloys. The procedure involves chromium acetylacetonate extraction using methyl isobutyl ketone followed by direct atomic absorption analysis of the organic extract. The detection limit of the procedure is 10 ng g⁻¹. Correspondence: Konstantin Belikov, State Scientific Institution “Institute for Single Crystals” of the National Academy of Sciences of Ukraine, Kharkov, Ukraine     

Simultaneous determination of heavy metals in waters by inductively-coupled plasma atomic emission spectrometry after extraction into diisobutyl ketone

Nebulization of more than thirty aliphatic and aromatic liquids into a low power (<1.6 kW) argon inductively-coupled plasma (i.c.p.) was evaluated. Diisobutyl ketone (DIBK) was best owing to the ease of its introduction into the i.c.p. and low aqueous solubility. Dichloro-8-quinolinol, hexamethyleneammonium hexamethylenedithiocarbamate and ammonium pyrrolidinedithiocarbamate were tested for extraction ; the last was preferred as chelating reagent because it formed complexes with Cd, Pb, Zn, Fe, Cu, Ni, Mo and V at pH 2.4. These metals at μg l^-1 levels in river and sea water were extracted into DIBK and determined simultaneously by i.c.p. atomic emission spectrometry. The optimum observation height for the DIBK extract was higher than that for an aqueous solution.     

Aldehyde-selective addition of alkynylchromium compounds prepared by reduction of alkynyl halides with chromium(II) reagent

Alkynyl halides are reduced by chromium(II) chloride in DMF to give unisolable alkynylchromium compounds which add selectively to an aldehyde moiety without affecting the coexisting ketone group of the substrate.     

Use of microwave digestion and atomic absorption spectrophotometry to determine chromic oxide as a digestibility marker in feed, feces, and ileal content.

Most conventional digestion procedures, such as dry ashing and wet ashing, are tedious and labor intensive. Microwave digestion is a good alternative, because microwave dissolution is faster, safer, and simpler, and provides more controlled reproducible conditions than conventional methods. The purpose of this study was to develop a microwave digestion method for mineralizing meat and bone meal diets, feces, and ileal contents. Each sample was heated on a hot plate for 10 min, dry ashed at 65 degrees C for 4 h, and transferred into microwave vessels. Then, 10 mL 70% HNO3 was added. Samples were digested for 7, 10, and 20 min at 95, 90, and 85% power, respectively. After the heating cycle, 6 mL 30% H2O2 was added, and samples were returned to the microwave for a second heating cycle of 1 and 7 min at 95% and 90% power, respectively. Finally, chromium concentration was determined by flame atomic absorption spectrophotometry. The digestion method was validated by using a standard reference material, SRM domestic sludge 2781, with a certified chromium value of 195 +/- 9 micrograms/g. The value obtained in this study was 178 +/- 11 micrograms/g, for a difference of 17 micrograms/g. Spike recovery experiments resulted in 103.16 and 100.35% recoveries of chromium from diet and feces samples, respectively. Coefficients of variation were 10.8 and 7.8%, respectively.     

The simultaneous determination of vanadium,chromium, manganese,iron, cobalt,nickel, copper and zinc in sea water by x-ray fluorescence sectrometry

A procedure is described for the determination of microgram quantities of the elements vanadium, chromium, manganese, iron, cobalt, nickel, copper and zinc in sea water. Separation and concentration of these elements from a large salt matrix, in order to prevent interferences in the subsequent X-ray fluorescence spectrometry, is achieved by continuous solvent extraction. Ammonium pyrrolidine dithiocarbamate is used as a chelating agent, and the chelated trace elements are quantitatively extracted at a pH of ca. 2.5 into methyl isobutyl ketone. Detection limits of 0.14 μg or better are obtained when a 600-sec counting period is used for X-ray fluorescence spectrometry.     

Selective determination of airborne hexavalent chromium using inductively coupled plasma mass spectrometry

A new method for determining ultra-trace levels of hexavalent chromium in ambient air has been developed. The method involves a 24-h sampling of air into potassium hydroxide solution, followed by silica gel column separation of chromium (VI), then preconcentration by complexation and solvent extraction. The chromium (VI) complex was dissolved in nitric acid. The resultant chromium ions were determined by inductively coupled plasma mass spectrometry (ICP–MS) using a dynamic reaction cell (DRC) with ammonia as the reactive gas to reduce polyatomic interferences. The interconversion of chromium in potassium hydroxide solution and air sample matrix were investigated under ambient conditions. It was found that there was no conversion of chromium (VI) into chromium (III) species. However, it was observed that some chromium (III) species were converted into chromium (VI) species. For a KOH solution containing 100 μg l⁻¹ of chromium (III) species, the rate of conversion was found to be 3% after 24 h exposure, 8% after 48 h, 10% after 72 h and no further conversion was observed thereafter. However, in a solution containing air sample matrix, 9.3% of chromium (III) converted to chromium (VI) within 6 h, and during the course of a 11-day exposure period, 13% (range 8–17%) of chromium (III) converted to chromium (VI). The method detection limit (MDL) for chromium (VI) in potassium hydroxide solution (0.025 M) was found to be 2×10⁻² μg l⁻¹. This is equivalent to 0.2 ng m⁻³ (for 23 m³ air sampled into 200 ml of KOH solution over a 24-h period). The recovery of spiked chromium (VI) from solutions containing air sample matrix was 95±9% (n=8). Matrix related interferences were estimated to be less than 10% based on recovery studies. The concentration of airborne chromium (VI) in Sydney residential areas was found to be less than 0.2 ng m⁻³, however, in industrial areas the concentrations ranged from 0.2 to 1.3 ng m⁻³ using this analytical procedure.     

Rapid chelatometric estimation of chromium, iron and aluminium in chromium + iron and chromium + aluminium mixtures

Summary A study of the kinetics of the reaction of chromium(III) with EDTA [1,2] had shown that the rate of reaction, usually slow, can be accelerated in the presence of hydrogen carbonate, sulphite, nitrite and organic solvents like alcohols, ketone, dioxane, etc., or suppressed in the presence of oxalate, acetate, etc. Based on this principle, a rapid titrimetric method using EDTA was developed for the estimation of chromium(III), iron and aluminium in chromium(III) + iron and chromium(III) + aluminium mixtures. The method has been extended for the estimation of iron and chromium(III) in stainless steel. Results are satisfactory.

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Zusammenfassung Die Reaktion von Chrom(III) mit äDTA kann durch Hydrogencarbonat Sulfit, Nitrit sowie organische Lösungsmittel beschleunigt oder durch Oxalat, Acetat u. a. unterdrückt werden. Aufgrund dieser Erscheinung wurde ein chelatometrisches Verfahren zur Bestimmung von Chrom(III), Eisen und Aluminium in Gemischen von Cr + Fe oder Cr + Al ausgearbeitet, das auch auf die Bestimmung von Eisen und Chrom in rostfreiem Stahl angewendet wurde. Es wurden befriedigende Ergebnisse erhalten.

     

有机铬改善SD大鼠体组成效果及其机制探讨

为探讨两种形式有机铬吡啶羧酸铬（CrPic）和烟酸铬（CrNic）改善SD大鼠体组成的效果及其机制,将60只雄性SD大鼠随机等分为3组,第1组饲喂基础日粮作为对照组,第2和第3组分别以CrPic和CrNic形式添加300μg/kg铬,自由采食和饮水,6周后测定大鼠体组成和皮下脂肪组织中脂肪酸合成酶及激素敏感酯酶活性以及血清相关指标。结果表明,添加CrPic使大鼠瘦体质量提高了21．9％（P〈0．05）,体脂含量降低了22．6％（P〈0．05）;添加CrNic对大鼠瘦体质量和体脂含量没有产生显著影响（P〉0．05）;CrPic使大鼠皮下脂肪组织中脂肪酸合成酶活性降低了5．6％（P〈0．05）,激素敏感酯酶活性提高了63．1％（P〈0．05）,同时,大鼠血清中葡萄糖和胰岛素水平显著降低;CrNic对皮下脂肪组织中脂肪酸合成酶、激素敏感酯酶活性以及血清相关指标没有产生显著影响（P〉0．05）。提示CrPic能通过减弱机体脂肪合成代谢,增强脂肪分解代谢从而提高大鼠瘦体质量,降低体脂含量,其效果显著高于CrNic。     

Spectrophotometric determination of 0-50 ng of chromium in 1 ml of human serum

A method is described for the determination of chromium in 1 ml of human serum or plasma. It is based on a wet decomposition and a spectrophotometric determination with diphenylcarbazide after extraction with methyl isobutyl ketone. A 40-mm cuvette with less than 1 ml sample volume is described. Results are lower than expected from the literature, most samples from healthy persons containing less than 2 or 3 ng ml . The reproducibility is about 1 ng ml .