The separation of berkelium(III) from cerium(III)

Factors affecting the separation of Bk(III) and Ce(III) in liquid-liquid extraction by tertiary and quaternary amines from neutral solutions of Li, Na, NH₄ and K nitrates have been investigated. It has been found that the maximum separation factor is reached in the extraction from NaNO₃ solutions by solutions of methyl-containing alkylammonium nitrates in xylene.     

Simultaneous spectrofluorimetric determination of cerium(III) and cerium(IV) by flow injection analysis

Cerium(III) (1–100 μg l^?1) is determined by injection into a carrier stream of hydrochloric, perchloric or sulphuric acid, and monitoring its native fluorescence. Cerium(IV) can be determined similarly by incorporating a zinc reductor minicolumn into the system. Splitting the injection sample so that only part passes through the reductor, and the remainder by-passes it, allows total cerium and cerium(III) to be detected from the two sequential fluorescence peaks obtained.     

Determination of cerium(III) and cerium(IV) in nanodisperse ceria by chemical methods

Percentages of different valence cerium species have been determined in powdery samples, redispersible compositions, and aqueous sols of nanodisperse ceria prepared from cerium(IV) and cerium(III) salts by various methods with or without organic stabilizers. Cerium(III) is shown to be virtually absent in nearly all of the CeO₂ samples studied. Organic stabilizers are shown to be capable of reducing cerium(IV) in aqueous CeO₂ sols.     

Determination of trace aluminum (III) using a novel cerium (IV)-calcein chemiluminescence detection

A simple, sensitive and selective chemiluminescence (CL) method was developed for the direct determination of aluminum (Al). This method is based on that the weak CL of cerium (IV)-calcein can be greatly enhanced by Al(III). The calibration curve was linear over the range 2.0 x 10(-10) to 4.0 x 10(-8)g mL(-1) with a detection limit of 8 x 10(-11)g mL(-1) (3sigma). The R.S.D. was 2.5% by 11 replicated determinations of 1.0 x 10(-9)g mL(-1) Al(III). The proposed method has been used to determine the concentration of Al(III) in real water samples with satisfactory results. The mechanism of the CL reaction was also discussed.     

N-oxides of 4-(5-nonyl)pyridine and trioctylamine as extractants for cerium(IV) and its separation from thorium(IV)

Trace level cerium has been oxidized to the quadrivalent state with potassium dichromate and shown to be preferentially extracted from very dilute mineral acid solutions and also from moderate nitric acid media by 0.1M solutions of 4-(5-nonyl)pyridine oxide and trioctylamine oxide dissolved in xylene. The dependence of extraction on the type of N-oxide, acid concentration and the N-oxide concentration has been investigated. The influence of the concentration of salting-out agents is described. Separation factors for a number of metal ions relative to cerium(IV) are reported for 0.1 M 4-(5-nonyl)pyridine oxide/xylene-0.1M sulphuric acid system. The ratio of the D for Ce(IV) to that of Ce(III) is greater than 10⁵, and the D for Ce(IV) is much greater than that for thorium(IV). Separation of cerium(IV) from thorium has been achieved from 0.1M sulphuric acid solutions using 0.1M 4-(5-nonyl)pyridine oxide/xylene as an extractant.     

Kinetics and mechanism of ruthenium(III) catalyzed oxidation of tellurium(IV) by cerium(IV)

The reaction is zero order in cerium(IV), fractional order in tellurium(IV) and first oder in ruthenium(III). While the ionic strength has no effect, the rate increases with increasing [H⁺], and decreases with increasing [HSO ₄ ^– ]. H and S are 54.4 kJ mol^–1 and –60.3 JK^–1 mol^–1, respectively. A suitable mechanism is proposed.

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(IV), (IV) (III). , [H⁺] [HSO ₄ ^– ]. H S 54,4 ^–1 –60,3 ·^–1·^–1, . .

     

Iridium(III) catalyzed oxidation of cyclic ketones by cerium(IV)

IrCl₃which is considered to be a sluggish catalyst in alkaline media, was found to surpass the catalytic efficiency of even osmium and ruthenium in acidic media in the oxidation of cyclopentanone and 2-methylcyclohexanone by cerium(IV) sulphate in aqueous sulphuric acid medium. It was observed that the order of the reaction shows direct proportionality with respect to low concentrations of the oxidant and alcohols, but tends to become independent of concentration at higher concentrations. On increasing the concentrations of externally added Cl^-, H⁺ and Ce^IIIions, the rate of the reaction decreases sharply initially but the decrease in rate becomes less prominent as their concentration is increased. The rate of reaction is directly proportional with respect to IrCl₃concentrations. Kinetic data suggest that the production of Ce^III ion occurs before the rate-determining step. Parameters such as the energy of activation, free energy of activation and entropy data collected at five different temperatures suggest that cyclopentanone forms the activated complex more easily.     

Improved recovery of trace amounts of gold (III), palladium (II) and platinum (IV) from large amounts of associated base metals using anion-exchange resins

The adsorption and desorption behaviors of gold (III), palladium (II) and platinum (IV) were surveyed in column chromatographic systems consisting of one of the conventional anion-exchange resins of large ion-exchange capacity and dilute thiourea solutions. The noble metals were strongly adsorbed on the anion-exchange resins from dilute hydrochloric acid, while most base metals did not show any marked adsorbability. These facts made it possible to separate the noble metals from a large quantity of base metals such as Ag (I), Al (III), Co (II), Cu (II), ¶Fe (III), Mn (II), Ni (II), Pb (II), and Zn (II). Although it used to be very difficult to desorb the noble metals from the resins used, the difficulty was easily overcome by use of dilute thiourea solutions as an eluant. In the present study, as little as 1.00 μg of the respective noble metals was quantitatively separated and recovered from as much as ca. 10 mg of a number of metals on a small column by elution with a small amount of dilute thiourea solution. The present systems should be applicable to the separation, concentration and recovery of traces of the noble metals from a number of base metals coexisting in a more extended range of amounts and ratios.     

Improved recovery of trace amounts of gold (III), palladium (II) and platinum (IV) from large amounts of associated base metals using anion-exchange resins

The adsorption and desorption behaviors of gold (III), palladium (II) and platinum (IV) were surveyed in column chromatographic systems consisting of one of the conventional anion-exchange resins of large ion-exchange capacity and dilute thiourea solutions. The noble metals were strongly adsorbed on the anion-exchange resins from dilute hydrochloric acid, while most base metals did not show any marked adsorbability. These facts made it possible to separate the noble metals from a large quantity of base metals such as Ag (I), Al (III), Co (II), Cu (II), Fe (III), Mn (II), Ni (II), Pb (II), and Zn (II). Although it used to be very difficult to desorb the noble metals from the resins used, the difficulty was easily overcome by use of dilute thiourea solutions as an eluant. In the present study, as little as 1.00 microg of the respective noble metals was quantitatively separated and recovered from as much as ca. 10 mg of a number of metals on a small column by elution with a small amount of dilute thiourea solution. The present systems should be applicable to the separation, concentration and recovery of traces of the noble metals from a number of base metals coexisting in a more extended range of amounts and ratios.     

Catalytic spectrophotometric determination of trace amount of cerium(IV)

Based on a property that in dilute hydrochloric acid hydrogen peroxide oxidizes Ponceau S to fade and cerium(IV) has a catalytic effect on the reaction, a new spectrophotometric method was developed for the determination of trace cerium(IV). At 450 nm, the cerium(IV) concentration presents a good linear relationship over the range of 0.08?4 μg/mL with the fading degree ΔA. Its linear regression equation is ΔA = 0.0475c (μg/mL) + 0.0007, with a correlation coefficient of 0.9991. The detection limit of method is 0.05 μg/mL. The method has been successfully applied to the determination of cerium in water and molecular sieve samples with good results. The relative standard deviations of eleven determinations were 0.97?1.11 and 0.19?1.01%, respectively. The recoveries of standard additions were 99.4?99.9 and 99.2?101.0%, respectively. The reliability of this method was certified by parallel determination against the dibromo-p-chlorochlorophosphonazo spectrophotometry.     

Dissolution of cerium(IV)-lanthanide(III) oxides: comparative effect of chemical composition, temperature, and acidity

The dissolution of Ce(1-x)Ln(x)O(2-x/2) solid solutions was undertaken in various acid media in order to evaluate the effects of several physicochemical parameters such as chemical composition, temperature, and acidity on the reaction kinetics. The normalized dissolution rates (R(L,0)) were found to be strongly modified by the trivalent lanthanide incorporation rate, due to the presence of oxygen vacancies decreasing the samples cohesion. Conversely, the nature of the trivalent cation considered only weakly impacted the R(L,0) values. The dependence of the normalized dissolution rates on the temperature then appeared to be of the same order of magnitude than that of chemical composition. Moreover, it allowed determining the corresponding activation energy (E(A) ≈ 60-85 kJ·mol(-1)) which accounts for a dissolution driven by surface-controlled reactions. A similar conclusion was made regarding the acidity of the solution: the partial order related to (H(3)O(+)) reaching about 0.7. Finally, the prevailing effect of the incorporation of aliovalent cations in the fluorite-type CeO(2) matrix on the dissolution kinetics precluded the observation of slight effects such as those linked to the complexing agents or to the crystal structure of the samples.     

Extraction of thorium and cerium (III) chlorides by neutral organophosphorus solvents

Summary The extraction of thorium and trivalent cerium chlorides by tri-n-butyl phosphate and di-isoamylmethyl phosphonate has been investigated as a function of hydrochloric acid molarity in the aqueous phase and solvent concentration in the organic phase. The comparative stability of the extractable metal complexes with the two solvents has been also estimated. The second solvent has been recommended, instead of the first, for the separation of thorium and the rare earth elements from hydrochloric acid media.

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Zusammenfassung Die Extraktion von Thorium- und Cer(III)-chloriden mit Hilfe von Tri-n-butylphosphat und Di-isoamylmethyl-phosphonat wurde in Abhängigkeit von der HCl-Konzentration in der wäßrigen und der Lösungsmittelkonzentration in der organischen Phase untersucht. Die Stabilität der gebildeten Metallkomplexe wurde bestimmt. Zur Abtrennung von Thorium und Seltenen Erden aus salzsaurem Medium wird Di-isoamylmethyl-phosphonat empfohlen.

     

Determination of trace amounts of vanadium(IV) and (V) in water by energy-dispersive x-ray fluorescence spectrometry combined with preconcentration and separation

A method is described for the separation, preconcentration and quantitation of V(IV) and V(V) in water. Vanadium(V) is precipitated with diethyldithiocarbamate (DDTC) at pH 1.8 and V(IV) is precipitated with DDTC at pH 4. The precipitates are collected by vacuum filtration on a membrane filter for quantitation by energy-dispersive x-ray fluorescence spectrometry. Multi-element and single-element calibration curves are prepared and used to evaluate the matrix and mass effects of diverse ions such as Fe(III), Co(II), Ni(II), Cu(II), Zn(II) and Pb(II). The total amount of metal ions should not exceed about 100 μg. The V(IV) and V(V) are separated completely and recovered quantitatively.     

Extraction and separation of bismuth(III)

Separation of bismuth from beryllium, lead, iron(III), indium, scandium, lanthanum, antimony(III), zirconium, titanium, thorium, vanadium(V), molybdenum(VI), uranium (VI) and chromium(VI) is achieved by selective extraction of bismuth from 0.1M sodium salicylate solution (adjusted to pH 7) into mesityl oxide (MeO). The extracted species is Bi (HOC(6)H(4)COO)(3).3MeO. The results are accurate within +/- 0.5%, with a standard deviation of 0.8%. The separation and determination of bismuth takes only 15 min.     

The use of cerium(IV) phosphate for the gravimetric determination and separation of cerium

A method for the gravimetric determination of cerium as Ce₃(PO₄)₄ is described. Cerium can be separated from many metals in this form, as well as from permanganate and dichromate; the cerium separated can then be titrated with iron(II) solution. The method was verified for the determination of cerium in a rare earth concentrate.     

Solvent extraction of lanthanum(III) and cerium(III) with dialkyldithiophosphoric acids. Separation from thorium(IV)

The extraction of lanthanum(III) and cerium(III) with dialkyldithiophosphoric acids, Hdtp, into different polar and nonpolar solvents (cyclohexane, benzene, carbon tetrachloride, chloroform, diethyl ether, dibutyl ether, n-butanol and cyclohexanone) from aqueous solutions containing perchlorate, nitrate and chloride anions has been investigated. The effect of various factors, such as nature of the solvent, pH, metal concentration and foreign anions present in the aqueous phase was investigated in order to establish the mechanism of extraction process. The data obtained suggest an ion-exchange mechanism. The anions present in the aqueous phase do not participate in the extraction process and do not influence significantly the magnitude of the extraction ratios either. The extracted species in the organic phase is a 12 complex of lanthanide with Hdtp. The extraction efficiency (E%) is calculated and the possibility of Th-rare earths separation is discussed.     

Spectrofluorimetric determination of pharmaceutical compounds with the cerium(IV)—cerium(III) system

The compounds to be determined are oxidised by cerium(IV). The concentration of cerium(III) formed is measured spectrofluorimetrically. The method has been used both in solution and, by fluorodensitometry, on t.l.c. plates. Detection limits of some substances are 15 ng ml^-1 for the solution method and 5 ng per spot for the t.l.c. method.     

Fluorimetric trace determination of cerium(III) with sodium triphosphate

Sodium triphosphate acts as a specific reagent for enhancing the fluorescence intensity of cerium(III). The purpose of this study was to investigate the spectrofluorimetric determination of trace amounts of Ce(III) in sodium triphosphate solution. The excitation and emission wavelengths are 303.5 nm and 353 nm respectively. Optimum sodium triphosphate concentration is found to be 0.074 g l(-1) at room temperature. The fluorescence varies linearly with the concentration of cerium(III) in the range 0.001-45 mug ml(-1). The detection limit is 9.4 x 10(-4)mug ml(-1). The relative standard deviations for 30 mug ml(-1) and 0.05 mug ml(-1) Ce(III) in 0.074 g l(-1) sodium triphosphate solution are 1.1% and 0.72% respectively. Quenching effects of other lanthanides and some inorganic anions are described. This method is a direct and rapid analytical method for the determination of Ce(III) in rare earth mixtures and cerium concentrates.     

Oxidation of ketones by cerium(IV) in presence of iridium(III) chloride

Kinetic data, in iridium(III) chloride catalyzed oxidation of ethyl methyl ketone (EMK) and methyl propyl ketone (MPK) by cerium(IV) perchlorate in aqueous perchloric acid medium, suggest the formation of complex C₁ between cerium(IV) and organic substrate in the first equilibrium step, which in turn gives rise to another complex C₂ with the catalyst. This second complex in the rate-determining step gives rise to the intermediate products. Interestingly IrCl_3, which is considered to be a sluggish catalyst in alkaline media, was found to surpass the catalytic efficiency of even osmium and ruthenium in acidic media. Rate decreases in the beginning at low acid concentrations, but after reaching to a minimum it becomes directly proportional to acid concentrations. Probably on increasing the acid concentrations hydrolyzed species of ceric perchlorate gradually converts into the un-hydrolyzed species, which then accelerates the rate at higher [H⁺], resulting in the observed peculiar effect of hydrogen ions on the rate. Initial concentrations of cerium(IV) and acid determine the extent of reduction of cerium(IV) by water. Order of the reaction shows direct proportionality with respect to the oxidant and ketones at their low concentrations, but tends to become zeroth order at their higher concentrations. Rate of the reaction shows direct proportionality with respect to [IrCl₃] while change in ionic strength of the medium does not affect the reaction velocity. Parameters such as the energy of activation, free energy of activation and entropy data suggest that methyl propyl ketone forms the activated complex more easily compared to ethyl methyl ketone.     

Extraction and separation of thorium(IV) and praseodymium (III) with CYANEX 301 and CYANEX 302 from nitrate medium

Solvent extraction of Pr(III) and Th(IV) has been investigated with commercial extractants of CYANEX 301 (bis(2,4,4-trimethylpentyl) dithiophosphinic acid) and CYANEX 302 (bis(2,4,4-trimethylpentyl) monothiophosphinic acid) in kerosene from nitrate medium. The effects of various parameters affecting the extraction equilibrium of Th(IV) and Pr(III), including temperature, were studied and the stoichiometry of the extracted Th(IV) and Pr(III) species was elucidated. The separation of Th(IV) from Pr(III) depending on the difference in the extraction behavior of the two extractants towards these metals is given and discussed.This revised version was published online in November 2005 with corrections to the Cover Date.