Solvent extraction of metals with hydroxamic acids

Solvent extraction with hydroxamic acids has been investigated. with comparison of aliphatic and aromatic reagents for the extraction of iron, copper, cobalt and nickel. Caprylohydroxamic acid has been evaluated for use in extraction systems for titanium, vanadium, chromium, molybdenum and uranium, both in terms of acidity of aqueous phase and oxidation state of the metal. It has been established that caprylohydroxamic acid in 1-hexanol is a suitable extractant for the removal of titanium(IV), vanadium(V), chromium(VI), molybdenum(VI) and uranium(VI) from 6M hydrochloric acid.     

Coprecipitation with yttrium phosphate as a separation technique for iron(III), lead, and bismuth from cobalt, nickel, and copper matrices

The coprecipitation behavior of 44 elements (47 ions because of chromium(III,VI), arsenic(III,V), and antimony(III,V)) with yttrium phosphate was investigated at various pHs. Yttrium phosphate could quantitatively coprecipitate iron(III), lead, bismuth, and indium over a wide pH range; however, 18 ions, including alkali metals and oxo anions, such as vanadium(V), chromium(VI), molybdenum(VI), tungsten(VI), germanium(IV), arsenic(III,V), selenium(IV), and tellurium(VI), were scarcely collected. In addition, 19 ions, including cobalt, nickel, and copper(II), were hardly coprecipitated at pHs below about 3. Based on these results, the separation of iron(III), lead, and bismuth from cobalt, nickel, and copper(II) matrices was investigated. Iron(III), lead, and bismuth ranging from 0.5 to 25 μg could be separated effectively from a solution containing 0.5 g of cobalt, nickel, or copper at pH 3.0. The separated iron(III), lead, and bismuth could be determined by inductively coupled plasma atomic emission spectrometry using internal standardization. The detection limits (3σ, n = 7) of iron(III), lead, and bismuth were 0.008, 0.137, and 0.073 μg, respectively. The proposed method was applied to the analyses of metals and chlorides of cobalt, nickel, and copper.     

Determination of cobalt, nickel, lead, bismuth and indium in ores, soils and related materials by atomic-absorption spectrometry after separation by xanthate extraction

A method for determining approximately 0.5, mug/g or more of cobalt, nickel and lead and approximately 3 mug/g or more of bismuth and indium in ores, soils and related materials is described. After sample decomposition and dissolution of the salts in dilute hydrochloric-tartaric acid solution, iron(III) is reduced with ascorbic acid and the resultant iron(II) is complexed with ammonium fluoride. Cobalt, nickel, lead, bismuth and indium are subsequently separated from iron, aluminium, zinc and other matrix elements by a triple chloroform extraction of their xanthate complexes at pH 2.00 +/- 0.05. After the removal of chloroform by evaporation and the destruction of the xanthates with nitric and perchloric acids, the solution is evaporated to dryness and the individual elements are ultimately determined in a 20% v/v hydrochloric acid medium containing 1000 mug/ml potassium by atomic-absorption spectrometry with an air-acetylene flame. Co-extraction of arsenic and antimony is avoided by volatilizing them as the bromides during the decomposition step. Small amounts of co-extracted molybdenum, iron and copper do not interfere.     

Extraction and complexing of copper(II) with benzoic acid N,N-dihexylhydrazide

The solubility and acid-base properties of benzoic acid N,N-dihexylhydrazide (BDHH) were studied. The extraction of copper(II), cobalt(II), nickel(II), zinc(II), iron(III), platinum(II), platinum(IV), chromium(III), chromium(VI), palladium(II), and molybdenum(VI) with this reagent was studied. It was shown that BDHH most efficiently extracts copper(II) from ammonia solutions and chromium(VI) from sulfuric acid solutions. In the extraction of copper(II), complexes with the [Cu(II)]: [BDHH] = 1: 1 and 1: 2 stoichiometries were found to form. The structure of the 1: 2 complex was suggested proceeding from its IR spectra. A copper(II) extraction isotherm was plotted.     

Determination of tellurium in ores, concentrates and related materials by graphite-furnace atomic-absorption spectrometry after separations by iron collection and xanthate extraction

A method for determining approximately 0.01 mug/g or more of tellurium in ores, concentrates, rocks, soils and sediments is described. After sample decomposition and evaporation of the solution to incipient dryness, tellurium is separated from > 300 mug of copper by co-precipitation with hydrous ferric oxide from an ammoniacal medium and the precipitate is dissolved in 10M hydrochloric acid. Alternatively, for samples containing 300 mug of copper, the salts are dissolved in 10M hydrochloric acid. Tellurium in the resultant solutions is reduced to the quadrivalent state by heating and separated from iron, lead and various other elements by a single cyclohexane extraction of its xanthate complex from approximately 9.5M hydrochloric acid in the presence of thiosemicarbazide as a complexing agent for copper. After washing with 10M hydrochloric acid followed by water to remove residual iron, chloride and soluble salts, tellurium is stripped from the extract with 16M nitric acid and finally determined, in a 2% v/v nitric acid medium, by graphite-furnace atomic-absorption spectrometry at 214.3 nm in the presence of nickel as matrix modifier. Small amounts of gold and palladium, which are partly co-extracted as xanthates if the iron-collection step is omitted, do not interfere. Co-extraction of arsenic is avoided by volatilizing it as the bromide during the decomposition step. The method is directly applicable, without the co-precipitation step, to most rocks, soils and sediments.     

Determination of arsenic in ores, concentrates and related materials by graphite-furnace atomic-absorption spectrometry after separation by xanthate extraction

A method for determining approximately 0.2 mug/g or more of arsenic in ores, concentrates and related materials is described. After sample decomposition arsenic(V) is reduced to arsenic(III) with titanium(III) and separated from iron, lead, zinc, copper, uranium, tin, antimony, bismuth and other elements by cyclohexane extraction of its xanthate complex from approximately 8-10M hydrochloric acid. After washing with 10M hydrochloric acid-2% thiourea solution to remove residual iron and co-extracted copper, followed by water to remove chloride, arsenic is stripped from the extract with 16M nitric acid and ultimately determined in a 2% nitric acid medium by graphite-furnace atomic-absorption spectrometry, at 193.7 nm, in the presence of thiourea (which eliminates interference from sulphate) and palladium as matrix modifiers. Small amounts of gold, platinum and palladium, which are partly co-extracted as xanthates under the proposed conditions, do not interfere.     

Arsenic colorimetry with silver diethyldithiocarbamate

The effect of 22 interferences had been studied. Sulfur(II) must be oxidized by nitric acid; germanium, nitric acid, and perchloric acid must be removed by repeated evaporation with hydrochloric acid. Antimony, phosphate, selenium, tellurium, iron, tin, copper, nickel, and many other elements are eliminated by extraction of arsenic(III) chloride in concentrated hydrochloric acid with p-xylene or benzene. Metal ions forming complex or insoluble iodide can be blocked with an excess of potassium iodide. The method enables the determination of 2–30 μg of arsenic with a relative error <10%. It was tested with the materials of copper production.     

Determination of total chromium by flow injection analysis

The determination of total chromium by flow injection analysis is described. Cerium(IV) and nitric acid are used to convert chromium(III) to chromium(VI); the oxidation rate is enhanced by placing the reaction coil in an 80°C oil bath. 1,5-Diphenylcarbazide is used to form a colored complex with chromium(VI) that is measured at 540 nm. For both chromium(III) and chromium(VI), relative standard deviation of less than 1% is achieved with a sampling rate of 40 per hour. Linear response is obtained for 0.5–10 mg l^?1 chromium.     

Application of APCD/DIBK extraction system in strongly acidic media: Determination of traces of copper and nickel in titanium metals by extraction-flame atomic-absorption spectrometry

Extraction of nickel in strongly acidic solution (0.01 approximately 8M hydrochloric acid) with ammonium 1-pyrrolidinecarbodithioate (APCD) into di-isobutyl ketone (DIBK) has been studied, and the APCD/DIBK system has been applied to simultaneous extraction and flame atomic-absorption spectrometric determination of trace amounts of copper and nickel in titanium metal. Nickel could be extracted with copper from strongly acidic solution such as up to 5M hydrochloric acid with APCD/DIBK system. The extraction from such a strongly acidic media made it possible to extract nickel with copper, since it did not require the addition of a large amount of the masking agent which prevents the hydrolysis of the matrix titanium and also prevents the extraction of nickel. Thus, they could be extracted directly from the titanium metal sample digested by concentrated hydrochloric acid with a small amount of tetrafluorohydroboric acid. Effect of coexistence of a large amount (at least 0.2 g) of iron on the extraction of both elements could be prevented by keeping most of the matrix titanium as Ti(III). With the method described here, mug/g levels of copper and nickel in titanium metal could be rapidly determined with good precision and accuracy.     

Anion-exchange separations of metal ions in thiocyanate media

The analytical potential of a weak-base macroreticular anion-exchange resin for the quantitative separation of metal ions in thiocyanate media is investigated and demonstrated. Distribution data are given for the sorption of some 25 metal ions from aqueous mixtures of potassium thiocyanate (1.0M or less) and 0.5M hydrochloric acid. The magnitude of the distribution data suggests many possible separations, some of which were quantitatively performed by procedures which are fast, simple and require only mild conditions. Representative separations are removal of traces of iron(III) and copper(II) from water samples prior to the determination of water hardness (calcium and magnesium), separation of nickel(II) from vanadium(IV) and the separation of thorium(IV) from titanium(IV). Some multicomponent separations are the separation of rare earths(III) and thorium(IV) from scandium(III) and the separation of rare earths(III) from iron(III) and uranium(VI).     

Zur photometrischen Bestimmung kleiner Selenmengen

Summary Selenium(IV) or selenium(VI) is reduced in hydrochloric acid solution by means of chromium(II) to hydrogen selenide, which is passed into alkaline [Fe(CN)₆]^3– solution in a stream of nitrogen to be oxidized there to selenium(IV). 6 mol of [Fe]CN₆]^4– are formed per 1 mol of selenium. The latter reacts with iron(III) in the presence of 1,10-phenanthroline or bathophenanthroline-disulphonic acid to their Fe(II) complexes. The extinction coefficient for the determination of selenium is 68030 or 135700 1 · mol^–1 · cm^–1, respectively.     

Determination of selenium(IV) and other forms of selenium dissolved in sea water by anion-exchange resin loaded with sulfonic acid derivative of bismuthiol-II and hydride generation atomic-absorption spectrometry

Summary A sulfonic acid derivative of bismuthiol-II (bisIIS) was synthesized from 4-hydrazinobenzene sulfonic acid and carbon disulfide. Selenium(IV) was adsorbed selectively and quantitatively on the anion-exchange resin loaded with bis-IIS. Selenium adsorbed on the resin was eluted by the use of penicillamine and determined by hydride generation atomic absorption spectrometry (hydride generation/AAS). Selenium(VI) and other forms of selenium, which were not adsorbed onto the resin, were collected on the resin after digestion with nitric acid followed by reduction with hydrochloric acid. Separative preconcentration of selenium(IV), selenium(VI) and other forms of selenium in 0.5 mol/l sodium chloride could be carried out successfully by the proposed procedures. However, in the case of estuarial sea water containing a large quantity of organic substances, selenium(IV) could not be separated, because organic substances interfered with the reduction of selenium(VI) to selenium(IV) by the use of hydrochloric acid. Selenium(IV) and total amount of selenium(VI) and other forms of selenium dissolved in polluted sea water samples were determined by the proposed procedures.

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Bestimmung von Selen (IV) und anderen in Meereswasser gelösten Selenformen mit Hilfe eines mit dem Sulfonsäurederivat von Bismuthiol-II beladenen Anionenaustauschers und der Hydrid-AAS

     

Spectrophotometric determination of germanium in ores, concentrates, zinc-processing products and related materials with phenylfluorone and cetyltrimethylammonium bromide after separation by iron collection and heptane extraction of germanium tetrachloride

A method for determining approximately 0.2 microg/g or more of germanium in ores, concentrates, zinc-processing products and related materials is described. The sample is decomposed by fusion with sodium peroxide and the cooled melt is dissolved in dilute sulphuric acid. Silica, if > 50 mg, is removed by volatilization with hydrofluoric acid. Germanium is separated from sodium salts by co-precipitation with hydrous ferric oxide, the precipitate is dissolved in 3M hydrochloric acid and germanium is subsequently separated from iron(III) and other co-precipitated elements by a single heptane extraction of germanium tetrachloride from approximately 9.4M hydrochloric acid. The extract is washed with 12M hydrochloric acid to remove residual iron(III), then germanium is stripped with water and determined spectrophotometrically with phenylfluorone in a 1.4M hydrochloric acid-0.002M cetyltrimethylammonium bromide medium in the presence of ascorbic acid as a reductant for co-extracted chlorine. The apparent molar absorptivity of the complex is 1.71 x 10(4) l.mole(-1).mm(-1) at 507 nm, the wavelength of maximum absorption. Up to 5 mg of tin(IV), 10 mg of antimony(V) and tungsten(VI) and approximately 50 mg of silica do not interfere. Germanium values are given for some Canadian certified reference ores, concentrates and iron-formation samples and for a metallurgical dust.     

A new spot test for cerium(IV)

Summary A new colour reaction for the detection of cerram(IV) which can be carried out both in a test tube and on a spot plate has been described. The test solution is treated with methylene blue in nitric acid solution (11) to form a rose-red colour. This simple procedure has an advantage over the existing tests in that it is applicable in the presence of oxidising agents like chromium(VI), vanadium(V), nitrate, perchlorate and of coloured ions like copper(II), cobalt(II), nickel(II), chromium(III), iron(III), vanadium(IV), uranium(VI).

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Zusammenfassung Eine neue, sowohl in der Eprouvette wie auf der Tüpfelplatte ausführbare Farbreaktion zum Nachweis von Cer(IV) wurde angegeben. Die Probelösung wird mit salpetersaurer Methylenblaulösung behandelt und gibt eine rosarote Färbung. Die Reaktion hat gegenüber bekannten Tests den Vorteil, in Gegenwart von Oxydationsmitteln wie Cr(VI), V(V), NO₃ ^–, ClO₄ ^– bzw. in Anwesenheit gefärbter Ionen wie Cu(II), Co(II), Ni(II), Cr(III), Fe(III), V(IV) oder U(VI) anwendbar zu sein.

     

Cation-exchange behaviour of uranium(vi) on amberlite ir-120 : Separation from mixtures

Quantitative studies are reported on the cation-exchange behaviour of uranium(VI) at the milligram level with Amberlite IR-120. Hydrochloric, nitric, sulphuric, perchloric, acetic and citric acids were tested as cluants; 200–300 ml of 2 N hydrochloric, nitric or sulphuric acid suffice for quantitative elution of 17 mg of uranium(VI) from a 1.4 cm X 14 5 cm bed The efficiency of the elutmg agents is discussed in terms of their elution constants Uranium is separated from thorium by selective elution, from zirconium, cerium(III), copper and nickel by converting the latter into suitable anionic complexes and from phosphate just by passing the mixture through the cation exchanger.     

Spectrophotometric determination of arsenic in concentrates and copper-base alloys by the molybdenum blue method after separations by iron collection and xanthate extraction

A method for determining 0.0001-1% of arsenic in copper, nickel, molybdenum, lead and zinc concentrates is described. After sample decomposition, arsenic is separated from most of the matrix elements by co-precipitation with hydrous ferric oxide from an ammoniacal medium. Following reprecipitation of arsenic and iron, the precipitate is dissolved in approximately 2 M hydrochloric acid and the solution is evaporated to a small volume to remove water. Arsenic(V) is reduced to the tervalent state with iron(II) and separated from iron, lead and other co-precipitated elements by chloroform extraction of its xanthate from an 11M hydrochloric acid medium. After oxidation of arsenic(III) in the extract to arsenic(V) with bromine-carbon tetrachloride solution, it is back-extracted into water and determined by the molybdenum blue method. Small amounts of iron, copper and molybdenum, which are co-extracted as xanthates, and antimony, which is co-extracted to a slight extent as the chloro-complex under the proposed conditions, do not interfere. The proposed method is also applicable to copper-base alloys.     

Determination of antimony in ores and related materials by continuous hydride-generation atomic-absorption spectrometry after separation by xanthate extraction

A continuous hydride-generation atomic-absorption spectrometric method for determining approximately 0.02 mug/g or more of antimony in ores, concentrates, rocks, soils and sediments is described. The method involves the reduction of antimony(V) to antimony(III) by heating with hypophosphorous acid in a 4.5M hydrochloric acid-tartaric acid medium and its separation by filtration, if necessary, from any elemental arsenic, selenium and tellurium produced during the reduction step. Antimony is subsequently separated from iron, lead, zinc, tin and various other elements by a single cyclohexane extraction of its xanthate complex from approximately 4.5M hydrochloric acid/0.2M sulphuric acid in the presence of ascorbic acid as a reluctant for iron(III). After the extract is washed, if necessary, with 10% hydrochloric acid-2% thiourea solution to remove co-extracted copper, followed by 4.5M hydrochloric acid to remove residual iron and other elements, antimony(III) in the extract is oxidized to antimony(V) with bromine solution in carbon tetrachloride and stripped into dilute sulphuric acid containing tartaric acid. Following the removal of bromine by evaporation of the solution, antimony(V) is reduced to antimony(III) with potassium iodide in approximately 3M hydrochloric acid and finally determined by hydride-generation atomic-absorption spectrometry at 217.8 nm with sodium borohydride as reluctant. Interference from platinum and palladium, which are partly co-extracted as xanthates under the proposed conditions, is eliminated by complexing them with thiosemicarbazide during the iodide reduction step. Interference from gold is avoided by using a 3M hydrochloric acid medium for the hydride-generation step. Under these conditions gold forms a stable iodide complex.     

Determination of silver, antimony, bismuth, copper, cadmium and indium in ores, concentrates and related materials by atomic-absorption spectrophotometry after methyl isobutyl ketone extraction as iodides

Methods for determining ~ 0.2 mug g or more of silver and cadmium, ~ 0.5 mug g or more of copper and ~ 5 mug g or more of antimony, bismuth and indium in ores, concentrates and related materials are described. After sample decomposition and recovery of antimony and bismuth retained by lead and calcium sulphates, by co-precipitation with hydrous ferric oxide at pH 6.20 +/- 0.05, iron(III) is reduced to iron(II) with ascorbic acid, and antimony, bismuth, copper, cadmium and indium are separated from the remaining matrix elements by a single methyl isobutyl ketone extraction of their iodides from ~2M sulphuric acid-0.1M potassium iodide. The extract is washed with a sulphuric acid-potassium iodide solution of the same composition to remove residual iron and co-extracted zinc, and the extracted elements are stripped from the extract with 20% v v nitric acid-20% v v hydrogen peroxide. Alternatively, after the removal of lead sulphate by filtration, silver, copper, cadmium and indium can be extracted under the same conditions and stripped with 40% v v nitric acid-25% v v hydrochloric acid. The strip solutions are treated with sulphuric and perchloric acids and ultimately evaporated to dry ness. The individual elements are determined in a 24% v v hydrochloric acid medium containing 1000 mug of potassium per ml by atomic-absorption spectrophotometry with an air-acetylene flame. Tin, arsenic and molybdenum are not co-extracted under the conditions above. Results obtained for silver, antimony, bismuth and indium in some Canadian certified reference materials by these methods are compared with those obtained earlier by previously published methods.     

Liquid-liquid extraction of niobium(V) in the presence of other metals with high molecular mass amines and ascorbic acid

A novel method is proposed for the solvent extraction of niobium(V). A 0.1M solution of Aliquat 336S in xylene quantitatively extracts microgram quantities of niobium(V) from 0.01M ascorbic acid at pH 3.5-6.5. Niobium from the organic phase is stripped with 0.5M nitric acid and determined spectrophotometrically in the aqueous phase as its complex with TAR. The method permits separation of niobium not only from tantalum(V) but also from vanadium(IV), titanium(IV), zirconium(IV), thorium(IV), chromium(III), molybdenum(VI), uranium(VI), iron(III), etc. Niobium from stainless steel was determined with a precision of 0.42%.     

Determination of antimony in concentrates, ores and non-ferrous materials by atomic-absorption spectrophotometry after iron-lanthanum collection, or by the iodide method after further xanthate extraction

Methods for determining trace and moderate amounts of antimony in copper, nickel, molybdenum, lead and zinc concentrates and in ores are described. Following sample decomposition, antimony is oxidized to antimony(V) with aqua regia, then reduced to antimony(III) with sodium metabisulphite in 6M hydrochloric acid medium and separated from most of the matrix elements by co-precipitation with hydrous ferric and lanthanum oxides. Antimony (>/= 100 mug/g) can subsequently be determined by atomic-absorption spectrophotometry, at 217.6 nm after dissolution of the precipitate in 3M hydrochloric acid. Alternatively, for the determination of antimony at levels of 1 mug/g or more, the precipitate is dissolved in 5M hydrochloric acid containing stannous chloride as a reluctant for iron(III) and thiourea as a complexing agent for copper. Then tin is complexed with hydrofluoric acid, and antimony is separated from iron, tin, lead and other co-precipitated elements, including lanthanum, by chloroform extraction of its xanthate. It is then determined spectrophotometrically, at 331 or 425 nm as the iodide. Interference from co-extracted bismuth is eliminated by washing the extract with hydrochloric acid of the same acid concentration as the medium used for extraction. Interference from co-extracted molybdenum, which causes high results at 331 nm, is avoided by measuring the absorbance at 425 nm. The proposed methods are also applicable to high-purity copper metal and copper- and lead-base alloys. In the spectrophotometric iodide method, the importance of the preliminary oxidation of all of the antimony to antimony(V), to avoid the formation of an unreactive species, is shown.