Precipitation from mixed solvents—I aluminium 8-hydroxyquinolate

The precipitation of aluminium 8-hydroxyquinolate from a buffered acetone-water system has been effected by the volatilisation of the acetone. The use of this procedure results in a precipitate with physical characteristics superior to that obtained in the conventional manner and allows more efficient separation from interfering cations. Separations of 10-mg quantities of aluminium from an equal amount of cadmium as well as separations of 25-mg quantities of aluminium from at least 420 mg of magnesium and twice that amount of calcium can easily be accomplished. These results compare favourably with those obtained by hydrolysis of 8-acetoxyquinoline. A procedure is described for the quantitative determination of 2–10 mg of aluminium.     

Examination of the hexamethylenetetramine procedure for separation of thorium from rare earths and for determination of thorium

An examination has been made of the efficiency of the gravimetric reagent hexamethylenetetramine in the separation of thorium from rare earths and in the determination of thorium. Losses to the filtrate, beaker and filter paper are evaluated as well as the extent of rare earth and other contamination of the thorium hydroxide precipitate. When hydroxylamine is used as the reducing agent to keep cerium in the tervalent state, excellent separations are obtained. The efficacy of the reagent is offset by the loss of small amounts of thorium to the precipitation vessel, the scavenging properties of the precipitate for silica and the difficulty in evaluating a true reagent blank.     

Trichlorophenoxyacetic acid as a reagent for the determination of Thorium

2:4:5-trichlorophenoxyacetic acid has been successfully used for the determination of thorium. It has been proved to a better reagent for thorium than 2:4-dichlorophenoxyacetic acid as it produces quantitative precipitation of thorium at a considerably lower pH value and can separate Th from a number of common elements, such as Ca, Ba, Sr, Zn, Co, Ni, Ti, U, etc. and cerite earths more effectively. Zr and Fe interfere, but iron may be removed by a convenient method. Direct weighing may be applicable for the estimation of thorium within the limites of experimental error,     

Hydrolysis of substituted 8-acetoxyquinolines

In the absence of metal ions, the hydrolysis of 2-methyl-8-acetoxyquinoline and of 5-chloro-8-acetoxyquinoline follow the same reaction paths as those of the parent ester 8-acetoxyquinoline, including an intramolecular catalysis by the quinoline nitrogen. Unlike the hydrolysis of the other esters, that of the 2-methyl compound appears not to be catalysed by metal ions, and this is consistent with the view that catalysis by a metal ion involves the formation of a 7-membered chelate structure.     

Inorganic analysis in organic solvents: Spectrophotometric determination of chromium following a chromatographic separation

A new method is described for the determination of chromium. In a suitable solution, trivalent chromium is precipitated as its 8-hydroxyquinolate, or 8-hydroxyquinaldate, in the presence of trivalent iron. The dried precipitate is dissolved in chloroform, and the solution, diluted once with benzene, is passed through an activated alumina Chromatographic column. The optical density of the eluate, containing the chromium complex only, is measured at 410 or 425 mμ with respect to the solvent. Aluminium, vanadium and cobalt interfere when 8-hydroxyquinoline is used as reagent; but when 8-hydroxyquinaldine is used, the method is unequivocal.     

Solid phase extractive preconcentration of thorium onto 5,7-dichloroquinoline-8-ol modified benzophenone

The preparation of solid reagent 5,7-dichloroquinoline-8-ol modified benzophenone for preconcentration of thorium is described. The thorium-5,7-dichloroquinoline-8-ol complex is quantitatively retained on benzophenone in the pH range 6.0-6.5. The solid mixture consisting of the metal complex together with benzophenone is dissolved in 5 ml of acetone and thorium content was established spectrophotometrically by using Arsenazo III procedure. Calibration graphs are rectilinear over the thorium concentration range 0.001-0.2 mug ml(-1). Five replicate determinations of 20 mug of thorium present in 1 l of sample solution gave a mean absorbance of 0.320 with a relative standard deviation of 2.9%. The detection limit corresponding to three times the standard deviation of the blank was found to be 0.0005 mug ml(-1). The developed procedure has been successfully utilized for the estimation of thorium content of pure Rare earth chloride solution collected from Indian Rare Earths (IRE) Limited, Alwaye.     

Copper catalysis of 8-acetoxyquinoline hydrolysis

The hydrolysis of 8-acetoxyquinoline in dilute acid solution has been found to be subject to copper^II catalysis. The catalysed reaction is first order in 8-acetoxyquinoline (as the free base), first order in copper ion, and first order in hydroxide ion. It is proposed that a copper chelate is a reaction intermediate in the hydrolysis.     

Determination of thorium isotopes in bastnaesite ores

A procedure for the determination of alpha-emitting thorium isotopes in bastnaesite ores has been developed. The refractory sample was completely decomposed by potassium fluoride fusion in a platinum crucible followed by transposition to a pyrosulfate fusion. The pyrosulfate cake was dissolved in HCl and the resulting precipitate dissolved in DTPA solution; thorium was coprecipitated as hydroxide using cerium present in bastnaesite as natural carrier. Thorium was then extracted into a TOPO solution, separated by using Dowex 1-X8 for anionic exchange, electrodeposited and finally analyzed by alpha-spectrometry. Thorium was also determined spectrophotometrically using Arsenazo as a colorimetric reagent. The thorium yield of the above discussed chemical procedure is more than 85%.     

Separation of some platinum group metal chelates with 8-hydroxyquinoline by various high-performance liquid chromatographic methods

Different HPLC methodologies are employed to evaluate the separation and determination of some platinum metals (Pt, Pd, Ir and Rh) after the formation of 8-hydroxyquinolate chelates. With the aim of reducing the number of steps in treating the samples, the method developed did not include the elimination of excess chelating reagent before the analysis of metal chelates. Reversed-phase (RP), non-aqueous reversed-phase (NARP) and normal-phase (NP) HPLC are compared. The RP-HPLC method only permits the quantitative separation of Rh and Pd from the excess reagent. A silica column can be used to separate Ir and Rh by NP-HPLC. The NARP-HPLC method allows for the effective separation of the four elements tested, but the high detection limit (90 ng) for platinum and the peak width do not favour its application for quantitative measurement. Platinum group metals can be quantitatively separated and determined by NP-HPLC using a cyano column in less than 15 min. The broad linear range of all the elements (between 1 and 500 ng) is superior to that which has been previously reported and the detection limits (1.0 ng for Pt, 0.3 ng for Pd, 1.0 ng for Ir and 0.3 ng for Rh) are slightly lower.     

Photochemical precipitation of thorium and cerium and their separation from other ions in aqueous solution

Thorium was precipitated from homogeneous solution by exposing solutions of thorium and periodate in dilute perchloric acid to 253.7 nm radiation from a low-pressure mercury lamp. Periodate is reduced photochemically to iodate which causes the formation of a dense precipitate of the basic iodate of thorium(IV). The precipitate was redissolved, the iodate reduced, the thorium precipitated first as the hydroxide, then as the oxalate and ignited to the dioxide for weighing. Thorium(IV) solutions containing 8-200 mg of ThO(2) gave quantitative results with a standard deviation (s) of 0.2 mg. Separations from 25 mg each of iron, calcium, magnesium, 50 mg of yttrium and up to 500 mg of uranium(VI) were quantitative (s = 0.25 mg). Separations from rare earths, except cerium, were accomplished by using hexamethylenetetramine rather than ammonia for the precipitation of the hydroxide. Cerium(III) was similarly precipitated and converted into CeO(2) for weighing. Quantitative results were obtained for 13-150 mg of CeO(2) with a standard deviation of 0.2 mg. Separations from 200 mg of uranium were quantitative. Other rare earths and yttrium interfered seriously. The precipitates of the basic cerium(IV) and thorium iodates obtained are more compact than those obtained by direct precipitation and can be handled easily. Attempts to duplicate Suzuki's method for separating cerium from neodymium and yttrium were not successful.     

Diphenic acid as an analytical reagent

Summary Diphenic acid behaves as a selective reagent for the estimation of thorium in presence of phosphate, arsenate, molybdate, alkaline, earths, copper, cadmium, lead, bismuth, tin, aluminium, chromium, nickel, cobalt, zinc, manganese, magnesium and palladium. Thorium can be successfully separated from the cerite earths by the reagent from solutions having thoria: earth oxide ratio 126 by single precipitation and by double precipitation when the above ratio is 144. The reagent can separate thorium from solutions having ThO₂U₃O₈ ratio upto 180 by double precipitation. The metal can also be recovered from monazite sands.Thanks are expressed hereby to Dr. A. K. Ghosal, Principal, Darjeeling Government College and Dr. A. K. Mukherjee of Indian Association for the Cultivation of Science, Calcutta, for their kind encouragement and to the Government of India, Ministry of Natural Resources and Scientific Research for a gift of Indian Monazite for analysis.     

A colorimetric determination of thorium

A colorimetric method for the determination of thorium is proposed. It is based upon the precipitation of thorium with a standard solution of oxalic acid and the subsequent reaction of the excess oxalic acid with a standard solution of potassium permanganate. The absorbancy of the remaining permanganate solution is directly proportional to the thorium present. The variables affecting this method have been critically studied. Reliable determinations can be made in the range of 3 to 30 mg of thorium in 1 cm cells when the colored solution is diluted to 250 ml. Most interfering substances can be removed by electrolysis in a mercury cathode cell or by the precipitation of thorium with potassium iodate.     

Purification of 233U from Thorium and Iron in the Reprocessing of Irradiated Thorium Oxide Rods

A two step precipitation using ammonium carbonate and oxalic acid as the precipitants for thorium and iron is developed for the purification of ²³³U. Ammonium carbonate is added to the feed to increase the pH of the solution. The effect of pH on the solubility of U, Th and Fe in an excess of ammonium carbonate is studied. This indicates that the solubility of Th and Fe is minimum at pH 7 and the recovery of uranium is maximum. The effect of the concentration of thorium and iron on the recovery of uranium at pH 7 is studied. This indicates that the ammonium carbonate precipitation tolerates 2 g/l of thorium and 10 g/l of iron keeping losses of uranium to a minimum. If the feed solution contains more than a tolerable concentration of thorium the precipitation is followed in two steps: (1) Bulk of the thorium is removed by oxalate precipitation, (2) the remaining thorium and iron in the supernatant are removed by ammonium carbonate precipitation. A flow sheet is proposed for the purification of ²³³U from thorium and iron present in a strip product concentrate obtained during the reprocessing of irradiated thorium rods.     

Direktthermometrische bestimmung von thorium und lanthan in gläsern

A rapid method is described for the determination of thorium and lanthanum in non-silicate glasses. It is suitable for routine use in a works laboratory. The samples are dissolved in nitric acid. The thorium content is calculated from the measured heat of precipitation of thorium iodate, and the lanthanum content by difference from the heat of precipitation of both thorium and lanthanum oxalates together. The apparatus is calibrated by using standard solutions of the two metal ions. The standard deviations for the middle of the range (around 250 mg of the oxides) were 3·1 mg for ThO₂ and 1·7 mg for La₂O₃. An analysis takes about 1·5 hr.     

Preparative,infrared and thermogravimetric studies of three scandium 8-hydroxyquinolinates

The preparation of 3 scandium 8-hydroxyquinolinates is reported. Two were prepared by precipitation from homogeneous solution using 8-hydroxyquinoline generated by hydrolysis of 8-acetoxyquinoline, and the third by a solid-phase reaction. The first precipitate was obtained at pH 6.5 as a lemon-yellow compound with the composition ScQ₃.HQ (Q == C₉H₆NO). The second chelate was obtained at pH 8.8 as a bright-yellow compound of composition (ScQ₃)₂.HQ. The third scandium 8-hydroxyquinolinate was obtained by a solid-phase reaction between the lemon-yellow compound ScQ₃.HQ and 8-hydroxyquinoline. The orange compound has the composition (ScQ₃)₂.3HQ. Infrared spectra and pyrolysis curves indicated that the 3 chelates have very similar structures.     

Nano-sized Co(II)-8-hydroxyquinolate complex thin film via surface layer-by-layer chemical deposition method: Optimized factors and optical properties

An extensive study was performed and reported for evaluation and optimization of the factors affecting thin film formation of nano-sized Co(II)-8-hydroxyquinolate complex by surface layer-by-layer chemical deposition method. The formation of uniform thin films of nano-crystalline metal complex is heavily dependent on several important factors. Variation in metal and ligand concentrations (1:1–1:3) was found to show insignificant contribution to the molar stoichiometric ratio of the synthesized thin film of nano-sized Co(II)-8-hydroxyquinolate. The number of dipping cycles (2–50) was characterized by strong influence on the thin film thickness. The dependence of the immersion time (2–50 s) was proved to influence the crystal growth and homogeneity of the thin film. The role of pH of metal and ligand solutions was identified by strong contribution in development and formation of deposited Co(II)-8-hydroxyquinolate complex thin film. Finally, the role of solvent on the thin film formation was also studied and evaluated. Metal analysis, SEM, EI-MS, FT-IR and TGA were applied as monitoring techniques of these factors. The optical properties of Co(II)-8-hydroxyquinolate complex were also studied and the complex thin films were characterized by the highest optical transition from π–π* or n, π* states with energy gap in the UV-range at 3.13 eV. The lowest optical transition resulted from d–d transition or metal centered transition with energy 1.5 eV while, the optical transition at 2.35 eV is the contribution of metal ligand or ligand metal transition. In the light of the optical measurement, Co(II)-8-hydroxyquinolate complex can be considered as an organic semiconductor with the potential applications in the design of organic light-emitting diodes (OLEMs).     

Application of ion-exchange separations to determination of trace elements in natural waters-IX: simultaneous isolation and determination of uranium and thorium

A method is described for the determination of uranium and thorium in samples of natural waters. After acidification with citric acid the water sample is filtered and sodium citrate and ascorbic acid are added. The resulting solution of pH 3 is passed through a 4-g column of Dowex 1 x 8 (citrate form) on which both uranium and thorium are adsorbed as anionic citrate complexes. Thorium is eluted with 8M hydrochloric acid and separated from co-eluted substances by anion-exchange in 8M nitric acid medium on a separate 2-g column of the same resin in the nitrate form. After complete removal of iron by washing with a mixture consisting of IBMK, acetone and 1M hydrochloric acid (1:8:1 v v ) and treatment of the resin with 6M hydrochloric acid, the uranium is eluted from the 4-g column with 1M hydrochloric acid. In the eluate thorium is determined spectrophotometrically (arsenazo III method) while fluorimetry is employed for the assay of uranium. The procedure was used for the determination of uranium and thorium in numerous water samples collected in Austria, including samples of mineral-waters. The results indicate that a simple relationship exists between the uranium and thorium contents of waters which makes it possible to calculate the approximate thorium content of a sample on the basis of its uranium concentration and vice versa.     

Preparation, characterization and application of thorium oxalate for sorption of plutonium and americium from aqueous solution

Synthetic inorganic exchangers exhibit good thermal and radiation stability. Thorium oxalate precipitate shows potential for co-precipitation of plutonium and americium from oxalate supernatant generated during plutonium oxalate precipitation. In the present study, efforts were made to prepare thorium oxalate precipitate to be used for column operation. Distribution ratios were determined to optimize conditions for sorption of plutonium and americium on thorium oxalate from nitric acid + oxalic acid solutions with composition similar to that of oxalate supernatant. Column experiments were also performed to evaluate the sorption capacity of thorium oxalate for plutonium and americium from the same medium. The result showed that, thorium oxalate prepared in 1.75M HNO₃ at 70 °C is suitable for column operations. These studies showed that plutonium and americium could be simultaneously removed from aqueous solutions with composition similar to plutonium oxalate waste using glass column packed with thorium oxalate and these nuclides could be recovered by eluting with 3M HNO₃.     

O-carboxyphenyl azo chromotropic acid (sodium salt) as an analytical reagent

Summary 0-carboxyphenyl azo chromotropic acid (sodium salt), named as chromotrope 2 C, is used as a new colorimetric reagent for the determination of micro amounts of thorium and aluminium. The blue-violet and red-violet complexes show maximum absorption at 590 nm and the colour systems obey Beer's law from 0.1 to 8 ppm for thorium and 0.1 to 1ppm for aluminium. However, their optimum concentration ranges are from 1.6 to 8 ppm for thorium and 0.2 to 0.8 ppm for aluminium, where the percent relative errors per 1% absolute photometric error are, respectively, 3.06 and 2.94. The composition of the complexes, as elucidated by the continuous variation method, suggests a metal to reagent ratio of 23 for thorium and a ratio of 11 for aluminium. The instability constants for the complexes are of the order of 4.044×10^–10 and 1.006 × 10^–6 at 30°C.Part I, see Z. analyt. Chem. 174, 197 (1960)     

Simultaneous Spectrophotometric Determination of Uranium and Thorium Using Arsenazo III by H‐Point Standard Addition Method and Partial Least Squares Regression

Simultaneous determination of uranium and thorium using arsenazo III as a chromogenic reagent at pH 1.70 by H‐point standard addition method (HPSAM) and partial least squares (PLS) calibration is described. Under optimum conditions, the simultaneous determinations of uranium and thorium by HPSAM were performed. The absorbencies at one pair of wavelengths, 649 and 669 nm, were monitored with the addition of standard solutions of uranium. The results of applying the HPSAM showed that uranium and thorium can be determined simultaneously with weight concentration ratios of uranium to thorium varying from 20:1 to 1:15 in the mixed sample. By multivariate calibration methods such as PLS, it is possible to obtain a model adjusted to the concentration values of the mixtures used in the calibration range. In this study, the calibration model is based on absorption spectra in the 600–750 nm range for 25 different mixtures of uranium and thorium. Calibration matrices contained 0.10–21.00 and 0.25–18.5 μg mL^?1 of uranium and thorium, respectively. The RMSEP for uranium and thorium were 0.7400 and 0.7276, respectively. Both proposed methods (HPSAM and PLS) were also successfully applied to the determination of uranium and thorium in several synthetic and real matrix samples.