Spectrophotometric determination of plutonium with chlorophosphonazo III

Summary Plutonium(IV) forms a Chlorophosphonazo III complex in 0.5–2M hydrochloric acid. Maximum absorbance occurs at 620 and 685 nm. Beer's law is obeyed over the range of 0–50g per 10 ml and the molar absorptivity is 3.7×10⁴ mol^–1 cm^–1 at 690 nm. Plutonium can be determined in the presence of fluoride, sulfate and phosphate. However, lanthanides, thorium, uranium and zirconium interfere seriously.

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Zusammenfassung Plutonium(IV) bildet in 0,5-bis 2-m Salzsäure mit Chlorphosphonazo III eine Komplexverbindung, deren Absorptionsmaxima bei 630 und 685 nm liegen. Bis 50 g/10 ml entspricht die Farbe dem Beer'schen Gesetz; die molare Extinktion bei 690 nm beträgt 3,7·10⁴l·Mol^–1·cm^–1. Plutonium kann damit in Gegenwart von F^–, SO₄ ^2– und PO₄ ^3– bestimmt werden. Lanthanide, Th, U und Zr stören jedoch ernstlich.

     

Spectrophotometric determination of the lanthanides with chlorophosphonazo III

The molar absorptivities of the lanthanide complexes with chlorophosphonazo III over the pH range 1-4 were found to increase with atomic number to maximum values near 7000 1.mole(-1).mm(-1) for holmium, erbium and thulium and then to decrease slightly for ytterbium and lutetium. The complexes were found to be stable for up to 65 hr. The addition of alkali metal salts depressed the apparent absorptivity of the complexes but no interference was observed for the phosphate ion.     

Complexation reactions between lanthanum,gadolinium, and ytterbium and reagents of Arsenazo III group on the surface of fibrous materials loaded with a Chelex 100 ion exchanger

The complex formation reaction between La(III), Gd(III), and Yb(III) with Arsenazo III, Arsenazo M, and Chlorophosphonazo III after adsorption on polyacrylonitrile fiber loaded with an ion exchanger with iminodiacetate groups Chelex 100 has been studied. The influence of medium acidity, duration of the contact of the solution with the adsorbent, the presence of masking agents, and the concentrations of ions on the analytical signals of complexes in the solid phase has been investigated. It has been shown that there is a possibility to perform sorption-spectroscopic determination of the total concentration of the indicated elements using Chlorophosphonazo and the sum of lanthanum and gadolinium with Arsenazo M after adsorption from malonic acid solutions.     

Sorption-spectrophotometric determination of zirconium and chromium(VI) from a single sample on a two-layer support using Arsenazo III and 1,5-diphenylcarbazide

The possibility of the sorption-spectrometric determination of zirconium(IV) and chromium(VI) from a single sample using a two-layer support made of polyacrylonitrile fiber filled with a PANF-KU-2 cation exchanger and PANF-AV-17 anion exchanger is studied. After sorption zirconium is determined with Arsenazo III on PANF-KU-2 and chromium is determined with 1,5-dipehnylcarbazide on PANF-AV-17. The sorption of zirconium and chromium is studied in the dynamic mode from solutions of HCl, HNO₃, and H₂SO₄ and the optimal conditions of the simultaneous sorption of zirconium on PANF-KU-2 and chromium on PANF-AV-17 from 0.25 M HCl is chosen. Diffuse reflection spectra of zirconium and chromium complexes have are on the solid phase and the conditions of zirconium determination are optimized. Calibration curves are linear in the range of zirconium and chromium concentration 0.005–0.025 μg/mL; the detection limits are 0.002 μg/mL. The selectivity of zirconium and chromium determination is tested in the presence of interfering ions. A procedure is developed for their determination from a single sample at zirconium to chromium ratios from 3: 1 to 1: 3.     

Phosphorus removal from wastewater using a lanthanum oxide-loaded ceramic adsorbent

Phosphorus removal is significant to prevent the eutrophication of water bodies. Adsorption is a promising method with many attractive advantages. An adsorbent is essential to the adsorption method. To investigate the absorption efficiency of lanthanum oxide-loaded ceramic granules, this study loaded lanthanum oxide onto ceramic granules in two different approaches and obtained two adsorbents called G1 and G2. The effects of the initial concentration of phosphorus, pH, temperature, and interfering anions on the phosphorus adsorption of G1 and G2 were investigated in laboratory experiments. When pH ranged from 3.0 to 8.0, the two adsorbents achieved the optimum phosphorus removal efficiency. At pH 4.0, the removal efficiencies of G1 and G2 were 98.1 and 99.8 %, respectively. Temperature fluctuation had an insignificant effect on removal efficiency. The effect of the presence of interfering anions on the adsorption efficiency was limited, i.e., <10 %. Comprehensive comparison showed that G1 exhibited better performance than G2. The Brunauer–Emmett–Teller specific surface area and total pore volume expanded after modification by 40 and ×6, respectively. The X-ray fluorescence results showed a 42 % (percentage by mass) lanthanum content in the modified adsorbents, some of which existed in the endoporus, whereas others were loaded onto the surface of the ceramic granules. The results of the Fourier Transform infrared spectrometry noted combinations between ceramic granulars and lanthanum oxide, and G1 adsorbed PO₄ ^3? from an aqueous solution.     

Flow injection spectrophotometric determination of calcium in rain and snow with chlorophosphonazo III

Summary A spectrophotometric flow injection technique for the determination of calcium based on its color reaction with chlorophosphonazo III(CPA-III) is described. The complex formation of CPA-III with calcium ions was carried out in the presence of 0.01 mol/l oxalate at pH 2.8. Most of the common foreign ions did not interfere. Only strontium, barium and rare earth metals interfered. Under the optimum conditions, the calibration curve was linear up to 1.2 ppm calcium and the detection limit was 0.01 ppm for a sample volume of 120 l. The relative standard variations for 0.4 and 1.0 ppm calcium were 0.354 and 0.352%, respectively. The method was successfully applied to the determination of calcium in rain and snow.     

Quantum-chemical study of lutetium,ytterbium, and gadolinium phthalocyaninates PcLnCl

Structural parameters and IR spectra of the (¹A₁//C_4v)-PcLuCl, (²B₂//C_4v)-PcYbCl, and (⁸A₂//C_4v)-PcGdCl molecules, (²A₂//C_4v)-Pc⁺LuCl, (3B₁//C_4v)-Pc⁺YbCl, and (⁹A₁//C_4v)-Pc⁺GdCl cations, (¹A_g//D_2h)-PcLuCl₂LuPc dimer, and PcLuCl···PcLuCl coaxial molecular pair have been simulated using the DFT (U) PBE0/SDD method. The PcLnCl (Ln = Lu, Yb, Gd) molecules have exhibited the equilibrium Ln–N bond length of 222, 223, and 230 pm, the Ln–Cl bond length of 245, 246, and 253 pm, the dipole moment of 4.73, 4.57, and 4.84 D directed from Cl to Ln, and ionization potential of 6.6 eV. β-Decay (¹A₁//C_4v)-Pc¹⁷⁷LuCl → (¹A₁//C_4v)-(Pc^177mHfCl)⁺ occurs with no significant change of the charge on the metal atom.     

Separation of gadolinium(III) and lanthanum(III) by nanofiltration-complexation in aqueous medium

A new method is proposed for the separation of gadolinium(III) and lanthanum(III) in aqueous medium by nanofiltration combined with a complexation step. First DTPA was chosen as ligand for a selective Gd(III)/La(III) complexation. Having investigated the influence of three factors (pH, temperature and amount of ligand) for the selective complexation of DTPA towards Gd(III) and La(III), the system is then combined with a nanofiltration separation process to remove 92% of initial Gd(III) and only 12% of initial La.     

Sorption-spectrophotometric determination of iron(II, III) with the use of organic reagents immobilized in a polymethacrylate matrix

The interaction of iron(II) with 2,2′-dipyridyl and 1,10-phenanthroline immobilized in a polymethacrylate matrix was studied. The optimum conditions of the complexation of iron(II) with the immobilized reagents and the chemical analytical properties of the complexes in the polymethacrylate matrix were determined. A sorption-spectrophotometric procedure was developed for the determination of iron(II) and the total of iron(II, III) after the reduction of iron(III) by ascorbic acid. The procedure with 2,2′-dipyridyl was used for the analysis of samples of tap, well, and mineral water and a solution of glucose.     

Direct spectrophotometric determination of rare earths in organic extracts with chlorophosphonazo III

The highly sensitive spectrophotometric determination of rare earths after extraction into di(2-ethylhexyl)phosphoric acid and trioctylamine is described. A sample of extract is diluted with n-butanol, the solution of chlorophosphonazo III in n-butanol is added, and the solution is made up to defined volume. Absorbance is measured at 660–665 nm against a reagent blank. The method is suitable for the study of the extraction of individual rare earths by different organic extrahents.     

Corrosion of gadolinium and ytterbium in LiCl-KCl melt

Corrosion of gadolinium and ytterbium in a molten eutectic mixture of lithium and potassium chlorides is studied in the present work using the gravimetry and EMF methods. It is found that the corrosion rate of ytterbium is 3–5 times higher than that of gadolinium under similar conditions. Satisfactory agreement between the current density values of gadolinium corrosion calculated on the basis of the results of the gravimetric data and the values of steady-state potentials points to the electrochemical mechanism of gadolinium corrosion in the LiCl-KCl melt.     

Repetitive determination of calcium ion and regeneration of a chromogenic reagent using chlorophosphonazo III and an ion exchanger in a circulatory flow injection system.

The spectrophotometric determination of Ca2+ with chlorophosphonazo III (CPN) has been carried out by a circulatory flow injection (FI) method. A cation-exchange mini-column for the on-line regeneration of the main reagent was incorporated in this FT system, allowing a repetitive determination of Ca2+. A solution of 4.0 x 10(-5) M CPN in a 0.05 M acetate buffer (pH 5.0) in a single reservoir (50 ml) was continuously circulated at a constant flow rate of 1.5 ml min(-1). Into the stream, an aliquot (20 microl) of a sample containing Ca2+ was quickly injected by means of a 6-way valve. The complex formed was monitored spectrophotometrically at 670 nm in the flow system. Then, the stream passed through a cation-exchange column, which was introduced after the flow-through cell. A successful ligand-exchange reaction of Ca2+ between the CPN reagent and a cation exchanger, as well as a simultaneous regeneration of the free reagent took place. The stream then returned to the reservoir. The regeneration and recycling of the CPN reagent allowed as many as 300 repetitive determinations of 2.5 mg l(-1) Ca2+ solutions with the same 50 ml circulating solution.     

Sequential spectrophotometric determination of water-soluble calcium and magnesium in soils using chlorophosphonazo I

Summary A new procedure has been developed for the sequential spectrophotometric determination of water-soluble calcium and magnesium in soils using CPA-I. Optimum conditions for the spectrophotometric determination, Beer's law range, sensitivity of the color reaction, precision and the interference of various foreign ions are reported. The composition of the complexes also has been determined.

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Spektrophotometrische Reihenbestimmung von wasserlöslichem Calcium und Magnesium in Bodenproben mit Chlorphosphonazo I

Zusammenfassung Ein neues Verfahren zur spektrophotometrischen Reihenbestimmung von wasserlöslichem Calcium und Magnesium in Bodenproben mit CPA-I wurde ausgearbeitet. Die optimalen Bedingungen für die spektrophotometrische Bestimmung, der Gültigkeitsbereich für das Beersche Gesetz, die Empfindlichkeit der Farbreaktion, die Genauigkeit und die Störung durch verschiedene Fremdionen wurden angegeben. Auch die Zusammensetzung des Komplexes wurde bestimmt.

     

Comparative study of the masking effect of various complexans in the spectrophotometric determination of uranium with arsenazo III and chlorophosphonazo III

Results are presented for the masking of 35 elements with the complexans DTPA, EGTA and TTHA in the spectrophotometric determination of uranium(VI) with Arsenazo III at pH 1.8 +/- 0.2 and with Chlorophosphonazo III at pH 1.1 +/- 0.2. The complexans EDTA and DCTA were found to be less suitable because at low pH they tended to precipitate. DTPA is shown to be especially attractive for masking other elements in the determination of uranium(VI) at low pH.     

Spectrophotometric determination of phosphate using lanthanum chloranilate

The spectrophotometric determination of phosphate using lanthanum chloranilate has been investigated. It is possible to determine 3–300 ppm of phosphate with an accuracy of ±2%, if suitable conditions are chosen. Chloride or nitrate ions do not interfere up to 400 ppm. Interference from sulphate ion can be compensated for by adding a large amount of sulphate both to the sample and to the standard solutions. This method is simpler, has less critical reaction conditions, and develops a much more stable coloration than the conventional heteropolyacid methods.     

Simultaneous spectrofluorimetric determination of europium, dysprosium, gadolinium and terbium using chemometric methods

A spectrofluorimetric method for the simultaneous determination of dysprosium, europium, gadolinium and terbium in ternary and quaternary mixtures by the use of pyridine-2,6-dicarboxylic acid as a chelating agent was developed. The influence of chemical variables affecting the analytical reaction was evaluated. A partial least-squares procedure and PC Quant software were used to assess data obtained from a variable number of calibration solutions and wavelengths. The ensuing method was validated by applying it to the analysis of synthetic ternary (Eu-Dy-Tb) and quaternary mixtures (Eu-Dy-Gd-Tb) over the concentration ranges 60-550 mug Eu l(-1), 30-400 mug Dy l(-1) and 30-400 mug Tb l(-1) in the former, and 20-220 mug Eu l(-1), 20-235 mug Dy l(-1), 25-230 mug Gd l(-1) and 75-230 mug Tb l(-1) in the latter. The results obtained by using the two quantitation procedures are compared. The relative errors in the determinations were less than 8% in most cases.