Thin Layer Chromatographic of Metal Ions in Oxalic Acid-Oxalate Systems

Abstract

The adsorption behaviour of 48 metal ions has been studied in Oxalic acid - Oxalate systems using silica gel - G layers. The effect of p_H on R_f values was also investigated. A plot of -log Ksp Vs. R_M and R_f shows the dramatic behaviour of Hg²⁺ ion in 0.1 M Potassium Oxalate + 0.1 M Ammonium Oxalate (1:1) system. A number of interesting separations have been achieved e.g., Fe³⁺ - Ti⁴⁺ zr⁴⁺ - Ti⁴⁺, ce⁴⁺ - La³⁺, zr⁴⁺ - Th⁴⁺, Te⁴⁺ - Se⁴⁺ and Zr⁴⁺ - Y³⁺ - La³⁺. Ti⁴⁺ and Nb⁵⁺ were separated from a mixture of number of ions.     

Chromatographic study of anionic complexes

Summary The diffusion of tartrate complexes of Cu²⁺, Co²⁺, Ni²⁺ and Cd²⁺ through filter paper strips has been examined using 50% and 60% ethanol as solvents. The R_f values are higher when 50% ethanol is used. When 50% ethanol is used, it is noted in the case of Cu²⁺, Co²⁺ and Ni²⁺ that the R_f values decrease with the addition of tartrate in the beginning. Then the value increases and finally becomes constant. In case of Cd²⁺ the R_f value decreases by the addition of tartrate. In 60% ethanol the R_f value does not change by small additions of tartrate but decreases with higher concentration of the complexing agent. In case of Cd²⁺ the R_f value becomes zero by increasing the concentration of tartrate.Part I: See Z. analyt. Chem. 159, 332 (1957/58).     

A new solvent system for the separation of Th4+, UO 2 2+ and Zr4+ in the presence of common anions by thin-layer chromatography

Summary A TLC method has been developed for separating Th⁴⁺, UO₂ ²⁺ and Zr⁴⁺ in the presence of some common anions using a dimethylamine/acetone/formic acid mobile phase. Capacity factors, separation factors and resolution for the separation of Th⁴⁺ from UO₂ ²⁺ have been evaluated. The effect of the pH of the sample on R_F values of Th⁴⁺, UO₂ ²⁺, Ni²⁺ and Cu²⁺ has also been examined.     

Chelation Ion Chromatography on DMSO Impregnated Silica Gel-G Layers: Specific Separation of Cd2+, W6+, and Zr4+ from Transitional Metal Ions

Abstract

Chelation ion chromatography of metal ions on DMSO impregnated silica gel-G layers in ether; DMSO: 1M HNO₃ (1:1); n-butanol: acetone: HNO₃ (6:6:1) and di-isopropyl ether: DMSO: THF systems having varying compositions, was performed. The zero R_f for a number of cations is explained in terms of precipitation and strong adsorption. It was possible to separate Cd²⁺, W⁶⁺, Zr⁴⁺, Zn²⁺ and VO²⁺ from numerous metal ions. A number of analytically important binary and ternary separations were also achieved and were found useful in synthetic alloy analysis.     

Treatment of radioactive and industrial liquid wastes by Eichornia crassipes

Chemical factors such as pH, concentration and temperature affecting the removal of UO₂ ²⁺, Th⁴⁺, Fe³⁺, Cu²⁺, Pb²⁺,Cd²⁺, Ni²⁺, MnO₄ ^- and phenol by Eichornia crassipes aquatic plant from their solutions were examined. Maximum uptake of ions by Eichornia crassipes occurred at pH 4 to 6±0.5 at 25±3 °C. An initial rapid uptake phase for the first 6 hours followed by a slower near linear one was observed. One gram of Eichornia crassipes can accumulate about 25 mg UO₂ ²⁺, 5 mg Th⁴⁺, 30 mg Fe³⁺, 10 mg MnO₄ ^-, 15 mg Cu²⁺, 1.0 mg Pb²⁺, 1.5 mg Ni²⁺, 0.7 mg Cd²⁺ and or 25 mg of phenol.     

Chromatographic study of anionic complexes

Summary In this paper the variation of diffusion, through filter paper strips by the ascending method, of citrate complexes of Cu²⁺, Ni²⁺, Co²⁺ and Fe³⁺ has been studied using 50%, 55% and 60% ethanol as solvents. The R_f value is found to be less with higher concentrations of ethanol used. It has been noted that with 50% ethanol the R_f value increases with the addition of citrate and finally tends to become constant with high concentrations of citrate ions. In 55% ethanol the R_f value becomes constant at a later stage. In 60% ethanol it is noted that the R_f value does not change with small additions of citrate, but on increasing its concentration the R_f value begins to diminish.Part II see Z. analyt. Chem. 165, 81 (1959).     

Potential oscillations in the course of galvanostatic oxidation of hydrogen at platinum electrode in the presence of electrosorbing cations

An assumption has been made that in the presence of electrosorbing cations potential oscillations should be observed in the course of galvanostatic oxidation of hydrogen on platinum electrode. The reality of this assumption has been proved in the presence of Cd²⁺, Cu²⁺, Sn²⁺, Bi³⁺, Ag⁺ ions using different base electrolytes (H₂SO₄, HCl, HClO₄). Some features connected with these oscillation phenomena were considered.     

Studies on the Uptake of Rare Earth Elements on Polyacrylamidoxime Resins from Natural Concentrate Leachate Solutions

Synthesis of poly(acrylamidoxime) resin from polyacrylonitrile performed with different crosslinking ratios 2, 5, and 10 wt% of divinylbenzene as crosslinking agent, using methylbenzoate and dioctylphthalate as pore producing solvent, the reaction mixture occurred under nitrogen. Studies carried out on diluted solution from rare earth elements (REEs) concentrate contains impurities as Cu²⁺, Ni²⁺, Zn²⁺, Fe³⁺, Al³⁺, Si⁴⁺, Th⁴⁺, U⁶⁺, Ca²⁺, and K⁺. Changing some parameters as pH of the solution, time of feeding and type of acid as HCl, HNO₃, H₂SO₄. The adsorption efficiency of resin is in the order pH 6 > pH 5 > pH 4 > pH 2 with excluding pH 6 due to the precipitation of some of REEs with the impurities and complete precipitation of Dy ion during pH adjustment, the adsorption in HNO₃ > HCl > H₂SO₄ media.     

Crystal structure of the new thorium intermetallics Thin and Th6Cd7

The title phases are orthorhombic: ThIn,oP24, space groupPbcm,a = 10.806(3)A?,b = 9.954(4)A?,c = 6.520(4)A?,Z = 12; Th₆Cd₇,oP26, space groupPbam,a = 11.703(3),A?,b = 9.929(7)A?,c = 6.041(2)A?,Z = 2. Direct methods were used for both structure solutions on data collected with an automated single crystal X-ray diffractometer. Anisotropic refinements gaveR = 0.065for ThIn andR = 0.086for Th₆Cd₇ using 799 and 1015 reflections, respectively. The structure of ThIn is closely related to the hexagonal Ti₅Ga₄ type, from which it can be geometrically derived. Th₆Cd₇ can be regarded as a tetrahedrally close packed structure where the Th atoms present the typical CN 14, CN 15, and CN 16 Frank-Kasper polyhedra and the Cd atoms are icosahedrally coordinated.     

Role of stannic phosphate in the uptake of cations. Separation of zirconium from thorium and cadmium from indium at tracer concentrations

The uptake of Na⁺, K⁺, Rb⁺, Cs⁺, Ag⁺, Ca²⁺, Cu²⁺, Sr²⁺, Cd²⁺, Ba²⁺, Pb²⁺, Sc³⁺, Co³⁺, Y³⁺, Sb³⁺, Tb³⁺, Zr⁴⁺ and Th⁴⁺ cations at very small concentrations has been studied over a column of stannic phosphate. The exchanger was prepared by mixing H₃PO₄, NaCl and SnCl₄ in suitable proportions and the ratio of PSn, in the product was obtained to be 1.96. Radiochemical separations of carrier free⁹⁵Zr from²³⁴Th and^115mIn, from¹¹⁵Cd have been carried out by adopting a simple chemical procedure over a column of stannic phosphate. The -spectrum analysis showed that the separated products are of high radionuclidic purity. The separation procedures took less than half an hour with quantitative yield.     

Separation of uranium from thorium on cryptomelane-type hydrous manganese dioxide

The distribution of UO ₂ ²⁺ and Th⁴⁺ in nitric acid media on crypomelane-type hydrous manganese dioxide (CRYMO) has been investigated by batch equilibrations and column break-through techniques. The parameters studied involve the media composition and concentrations of HNO₃, NaNO₃, UO ₂ ²⁺ and Th⁴⁺. It is found that Th⁴⁺ is more strongly adsorbed on CRYMO than UO ₂ ²⁺ with sufficient differences for chromatographic separation from each other. Uranium was quantitatively eluted from a CRYMO column with 0.1M HNO₃. Th⁴⁺ has been recovered by using 1M HNO₃ as eluent.     

Studies on the ion-exchange behaviour of chromium ferrocyanide

The sorption of univalent, bivalent and trivalent ions has been studied on chromium ferrocyanide gel. The studies reveal a high sorption capacity for Cs⁺, Tl⁺, Ag⁺, Cu²⁺, Zn²⁺, Cd²⁺, Fe³⁺ and Th⁴⁺. The sorption of monovalent cations show purely ion-exchange mechanism while the uptake of bivalent and trivalent cations is non-equivalent in nature. Single elution of Rb⁺, Cs⁺ and Tl⁺ has been performed from the columns of this exchanger and the recovery is almost complete in all the cases. Cu²⁺ and Ag⁺ get completely adsorbed on the gel column and their elution is not possible probably due to the formation of some new solid phases. Depending on the K_d values of the metal ions, a large number of separations of radiochemical as well as analytical importance can be performed on the columns of this exchanger material.     

Lattice polarization effects in electrochromic switching in WO3−x films studied by pulse-nanogravimetric technique

The interactions of various types of cations with the tungsten trioxide lattice have been investigated to evaluate possible intercalation of these cations and the occurrence of lattice polarization leading to the near-surface structural lattice damage. The interactions of cations, such as the large monovalent cations (K⁺, Et₄N⁺, CtMe₃N⁺ cations), transition metal dications (Ni²⁺), heavy metal ions (Cd²⁺), and representative lanthanides (La³⁺) and actinides (Th⁴⁺), in competition with intercalation of H⁺ ions have been investigated using pulse-nanogravimetric technique. The effects of these cations in electrochromic processes of WO₃ proceeding during cathodic reduction have been assessed. For all of the metal ions studied, a large increase in the apparent mass uptake (up to eightfold) in comparison to pure H⁺ ion ingress was observed upon the film coloration induced by a cathodic potential pulse. The experiments indicate that the apparent mass gains, although large, are insufficient to confirm predominant contribution of metal ions in the ion transport along the channels in WO₃ lattice. The lower decoloration rate in the case of Ni²⁺ ions, in comparison to H⁺ and other transition metal cations (Cd²⁺), has been attributed to a slow dissociation of Ni²⁺ ions from lattice-bound oxygen atoms. For et₄N⁺ cation, which is too large to enter channels in WO₃, a dissociative reduction of the WO₃ and severe lattice damage was observed. Among the metal ions investigated, only K⁺ ions have been found to cause a dissociative reduction of WO₃ and near-surface lattice damage. Strong lattice polarization effects and irreversible binding have been found for La³⁺ and Th⁴⁺ cations.     

Toxic metal complexes of macrocyclic cyclen molecule – synthesis,structure and complexing properties

Toxic metal (Cd²⁺, Hg²⁺, Pb²⁺, and Ag⁺) complexes with the tetradentate macrocyclic ligand - cyclen (1,4,7,10-tetraazacyclododecane, [12]aneN₄, L) were prepared and studied in the solid state by IR, X-ray diffraction, elemental and thermal analysis. Diffraction results have yielded three molecular structures, [Cd([12]ane-κ⁴N^1,4,7,10)(NO₃)₂)] (1), [Hg([12]ane-κ⁴N^1,4,7,10)(NO₃-κ²O,O`)]NO₃ (2), [Pb₂([12]ane-κ⁴N^1,4,7,10)₂][Pb(NO₃)₆] (3) and one polymeric structure {[Ag₂([12]ane-κ³N^1,4,7)(μ₂-[12]aneN¹⁰)](NO₃)₂?2H₂O)}_n (4) featuring a unique coordination mode not observed before with cyclen as a ligand. The monodentate (1) and chelate (with small bite angle 50.3(3)°, (2) coordination modes of nitrate ligands were confirmed. Stereochemically active 6s² lone pair was suggested in 3 and DFT results confirmed no significant metal–metal covalent bond. The stability constants of the complexes with Cd²⁺ and Pb²⁺ ions were determined by potentiometric methods in aqueous solutions. Additionally, the structures of complexes in solution were observed by ¹H NMR. Both methods confirm similar cyclen complexing properties toward Zn²⁺ biometal and Cd²⁺, Pb²⁺ toxic metals.     

Anion-exchange separation of thorium and protactinium from uranium matrix

Summary The distribution behaviour of Th⁴⁺, Pa⁵⁺, and UO₂ ²⁺ ions between the anion-exchanger Amberlite IRA-400 and acetic acid-hydrochloric acid mixtures, has been investigated. It was found that the general behaviour of Th⁴⁺ ions is similar to that of UO₂ ²⁺ ions though the latter are much more highly adsorbed by the resin than Th⁴⁺. Protactinium exhibited a different behaviour from both Th⁴⁺ and UO₂ ²⁺ ions. The separation factors were calculated, and a Chromatographic procedure for sequential isolation of each element was developed.

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Zusammenfassung Das Verteilungsverhalten von Th⁴⁺, Pa⁵⁺ und UO₂ ²⁺ zwischen dem Anionenaustauscher Amberlit IRA-400 und Gemischen aus Essigsäure und Salzsäure wurde untersucht. Das allgemeine Verhalten von Th⁴⁺ ist ähnlich dem von Uranylionen, wenngleich letztere von dem Harz viel stärker adsorbiert werden als Th⁴⁺. Protactinium zeigt ein abweichendes Verhalten im Vergleich zu Th⁴⁺ und UO₂ ²⁺. Die Trennfaktoren wurden berechnet und ein chromatographisches Verfahren zur Isolierung der angeführten Ionen entwickelt.

     

Preconcentration and recovery of uranium and thorium from Indian monazite sand by using a modified fly ash bed

Adsorption of uranium, as UO₂ ²⁺, and thorium, as Th⁴⁺, has been studied using a modified fly ash bed. Effects of pH and various ions like La³⁺, Fe³⁺, Ce⁴⁺, SiO₃ ^2- etc., have been examined. Synthetic mixtures of UO₂ ²⁺ and Th⁴⁺ in different concentrations were passed through the bed and eluted separately with various selective reagents viz. ammonium carbonate, sodium carbonate and acetic acid-sodium hydroxide buffer. Separations of these elements at ppm level are shown to be very effective. The separation of uranium and thorium in the presence of lanthanides in monazite sand has been studied successfully. In the analysis of monazite sand, the oxalate precipitation has been avoided. The method is simple and of very low cost. The modified fly ash bed can also be used to remove uranium from contaminated water.     

Ion exchangers containing phosphorus in their functional group

Summary Uranium or thorium separations from a number of various ions were studied by means of cation exchangers containing phosphorus in their functional group. These ion exchangers adsorb selectively only UO₂ ²⁺ or Th⁴⁺ ions from the mixture studied in a medium of >0.4 N nitric or hydrochloric acid. Several di- and trivalent cations are not sorbed under these conditions. In the absence of UO₂ ²⁺ and Th⁴⁺ ions, Me²⁺ may be more easily separated quantitatively from Me³⁺ in 0.2 N nitric or hydrochloric acid than with cation exchangers containing the -SO₃H group.

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Zusammenfassung Die quantitative Trennung von UO₂ ²⁺ oder Th⁴⁺ von einer Reihe anderer Ionen wurde mit Hilfe phosphorhaltiger Kationenaustauscher untersucht. Diese Ionenaustauscher sorbieren selektiv nur UO₂ ²⁺ oder Th⁴⁺-Ionen aus einem Medium von >0,4 N HNO₃ oder HCl. Eine Reihe verschiedener zwei- und dreiwertiger Kationen wird unter diesen Bedingungen nicht sortiert. Bei Abwesenheit von UO₂ ²⁺- und Th⁴⁺-Ionen kann man Me²⁺ in 0,2 N HNO₃- oder HCl-Lösung quantitativ von Me³⁺ trennen, und zwar leichter als mit -SO₃H-haltigen Austauschern.

     

Die durch Blei(II) und Kupfer(II) katalysierte Zersetzung von Wasserstoffperoxid als Endpunktindikation chelatometrischer Titrationen

Zusammenfassung Die Anwendung der durch Blei(II) und Kupfer(II) katalysierten Zersetzung von Wasserstoffperoxid als exotherme Indikatorreaktion bei katalytisch-thermometrischer Endpunktindikation chelatometrischer Bestimmungen wird gezeigt. Die katalytische Wirkung von Blei(II) wird in ammoniak-ammoniumtartrathaltiger Lösung (p_H 12) und die Wirkung von Kupfer(II) in ammoniumcarbonathaltigem (p_H 8,8), natriumhydroxid-natriumcarbonathaltigem (p_H 10) und in ammoniakalischem Medium herangezogen. Die direkte Titration von ÄDTA, DCTA und NTA mit Kupfer(II) und Blei(II), die inverse Titration dieser Metalle, wie auch die Bestimmung einiger Metallionen (Zn²⁺, Cd²⁺, Cu²⁺, Ni²⁺, Pb²⁺, Bi³⁺, In³⁺, Th⁴⁺) durch Rücktitration wird beschrieben. Die genannten Ionen können im Milligramm- und Mikrogrammbereich mit befriedigender Genauigkeit bestimmt werden.

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The end-point indication of chelatometric titrations by the decomposition of hydrogen peroxide catalyzed by lead(II) and copper(II)

Summary The application of the decomposition of hydrogen peroxide as exothermic indicator reaction catalyzed by lead(II) and copper(II), to catalytic thermometric endpoint detection of chelatometric titrations is described. The catalytic action of lead(II) is applied in ammonia-ammonium tartrate solution (p_H 12), the action of copper(II) in ammonium carbonate (p_H 8.8), sodium hydroxide-sodium carbonate (p_H 10) and in ammoniacal medium (p_H 12). The direct titration of EDTA, DCTA and NTA with copper(II) and lead(II), the invers titration of this metals, as well as the determination of several ions (Zn²⁺, Cd²⁺, Cu²⁺, Ni²⁺, Pb²⁺, Bi³⁺, In³⁺, Th⁴⁺) by backtitration has been developed. The ions mentioned can be determined in the milligram and in the microgram range with reasonable accuracy.

     

Analytical aspects of some organic acids

Summary o-Phenylenedioxydiacetic acid has been found to be a selective reagent for the estimation of zirconium. As little as 2.1 mg of zirconium can be easily estimated. The composition of the precipitate varies somewhat and therefore, direct weighing is not possible. This difficulty is overcome by igniting as oxide. Be²⁺, Ca²⁺, Ba²⁺, Zn²⁺, Hg²⁺, Al³⁺, Ce³⁺, Ti⁴⁺, Th⁴⁺, UO²⁺, Mn²⁺, Fe³⁺, Co²⁺, and Ni²⁺, ions do not interfere. Although V₂O₂ ⁴⁺ and Cr³⁺ ions are not precipitated in neutral or slightly acidic solutions they contaminate the zirconium precipitate, at about 0.30 N HCl concentration. The amount of contamination is so small that it is removed by double precipitation. This method gives satisfactory results even in the presence of small amounts of SO₄ ^2–ions.     

Spectrophotometric determination of molybdenum(vi) with benzoylacetanilide

Abstract

The complex formed between molybdenum(VI) and benzoylacetanilide in the pH range 0.6 and 1.9 has been extracted into methyl isobutyl ketone and the absorbance has been measured at 410 mμ. Quantities of 0.15 to 2.10 mg of molybdenum have been determined with a standard deviation of 0.6%. The color is stable up to 2 hours. The presence of Co²⁺, Ni²⁺, Zn²⁺, Mn²⁺, Be²⁺, Al³⁺, Cr³⁺, Ce⁴⁺, Th⁴⁺ or UO²⁺ ₂ up to 100 μg causes no interference. Ordinarily, Fe³⁺ interferes with the determination, but when masked with 1 ml of 0.5% solution of ascorbic acid the tolerance limit is 10 mg. Thus, molybdenum can be determined in steel when present in amounts as low as 0.26%.