Use of organic reagents in inorganic analysis

Summary Paper chromatography of cobalt, palladium, uranium, thorium, and zirconium/1-nitroso-2-hydroxy-3-naphtholates which are quantitatively precipitated, has been studied. As most of the complexes were not soluble in organic solvents, their hydrochloric acid solutions and solution of the cobalt, palladium, and uranium complexes in ammonium hydroxide were used for spotting. A large number of developing solvents were tried both on plain and salt-impregnated papers. A solvent mixture containing 60% acetone, 38% isobutyl alcohol and 2% 12N HCl, by volume was found suitable for the resolution of a mixture of complexes of cobalt, palladium, and uranium on plain paper. Thorium and zirconium complexes, however, did not move appreciably with any of the solvent mixtures tried. The paper impregnated with salt solutions did not show any improvement in the separation. The effect of HCl in the above solvent mixture on the separation of cobalt, palladium, and uranium, was also studied. It was observed that a small amount of HCl was necessary in this developing solvent for the migration of the metals, a large excess of this acid, increases their R_f values and these are brought so close that the separation of the metals becomes difficult. The colour of the cobalt, palladium, and uranium spots on the developed chromatograms indicated that the metals migrated as their complexes. Similar experiments were done with free metals ions, which gave different R_f values and this confirmed the fact that it was the metal complexes that moved and these complexes were stable under the conditions of the experiment. Precipitation of Co, Pd and U with 1-nitroso-2-hydroxy-3-naphthoic acid is quantitative and the paper chromatographic experiment affords a convenient method of concentrating the metal ions.Part IV: See Z. anal. Chem. 155, 241 (1957).     

Use of organic reagents in inorganic analysis

Summary Eighteen anilic acids have been prepared from maleic anhydride and various aromatic amines and their properties and analytical reactions with various metal ions have been studied. The acid prepared from benzidine was insoluble in all common solvents and, hence, its application could not be studied. Most of these reagents, except those obtained from aniline, o- and p-chloroanilines, nitranilines, p-amino-acetanilide and o-phenylenediamine, produced more or less quantitative precipitations with both thorium and zirconium. Their actions towards thorium and zirconium were very much alike. They also gave precipitations with mercury(I), lead and cerium(IV), but such precipitations were not complete. Ferrous iron showed greyish turbidity with most of the reagents, but ferric iron produced colourations varying from brown to violet, such colours were, however, found to be unstable either on standing for a while or on heating. Gold and platinum underwent reduction in presence of these reagents.Part VIII: See Z. analyt. Chem. 163, 403 (1958).The work has been carried out in the chemical laboratories of Darjeeling Government College, Darjeeling. The author is grateful to the authorities of the College for the laboratory facilities.     

Use of organic reagents in inorganic analysis

Summary Thorium and zirconium have been determined gravimetrically with phenylglycine-p-carboxylic acid and zirconium alone with phenylglycine-o-carboxylic acid, almost within the same pH range. Better results are obtained when zirconium is precipitated in acetic acid solution in presence of a little ammonium acetate. A number of foreign ions may be separated from thorium and zirconium with these reagents. Iron and titanium cause heavy interference. The interference caused by iron, may however, be eliminated by adding a little ascorbic acid, before precipitation of the metals. The para acid can also extract thorium from a mixture of cerite earths and from monazite sands.Part V: See Z. anal. Chem. 158, 347 (1957).The author likes to thank Dr. B. N. Bose, Principal of the College and Dr. S. K. Sinha, the Head of the Department of Chemistry for their kind advice and encouragements.     

Use of inorganic adsorbers in radium analysis

Two new simple methods were studied for the analysis of radium in fresh waters by concentration and purification. Both methods are based on the use of an inorganic selective adsorber, namely basic lead rhodizonate, LERHO, and partially reduced tin dioxide (PRTD). The procedures were checked by using filtered fresh waters spiked with 0.1 Bq of²²⁶Ra, and in the presence of few μg/l of barium. In each experiment¹³³Ba radioisotope was added to water samples to measure the yield of the overall procedure by γ-counting. Barium and radium were adsorbed from basic solutions on LERHO packed chromatographic column in the first procedure, while batch experiments were preferred for the adsorption on PRTD. After separation,²²⁶Ra and barium were eluted from the exchangers and co-precipitated onto small filters as thin film, supported on an inactive barium sulphate substrate, to be submitted to alpha-and gamma-spectrometry. Both methods gave promising results.     

Use of supercritical fluids in inorganic analysis

The possibilities, advantages, shortcomings, and prospects of using supercritical fluids for separating and extracting metal complexes with organic reagents are considered. The theoretical bases of supercritical fluid chromatography and factors influencing the separation of metal complexes (nature of the organic reagent, solubility of reagents and complexes in a supercritical fluid, type of column, motionless phase, addition of a modifier into the mobile phase, and the test solvent) are discussed. The processes occurring in complexes during chromatography are discussed. The bases of supercritical fluid extraction and factors influencing extraction of metals (nature and solubility in a supercritical fluid of an organic reagent and complexes; concentration and ways of introducing the reagent into the system; addition of the modifier, water, and surfactants; the collector; and the matrix) are considered. The possibilities of methods for determining metals in various objects are shown.     

Properties and construction of azo-dye reagents for inorganic photometric analysis

An approach to constructing new organic reagents (based on azo dyes) for photometric analysis is described. Its essence is the detailed consideration of the electronic structure of the chromophore nuclei of the dyes in the ground and excited states. Knowing the nature of the electron transition, it is possible to construct the organic reagents with optimal properties. The electronic structure of the azo dyes has been analysed in a pi-approximation by an MO LCAO SCF method.     

Use of organic reagents for the voltammetric determination of rare-earth elements

The data on organic reagents used for the voltammetric determination of rare-earth elements (REE) is surveyed. The mechanisms of the reduction of complexes formed by REE with some reagents are presented. Procedures for determining REE in real samples using organic reagents are briefly characterized.__________Translated from Zhurnal Analiticheskoi Khimii, Vol. 60, No. 4, 2005, pp. 342–348.Original Russian Text Copyright © 2005 by Dubenskaya, Levitskaya, Poperechnaya.     

锰试剂在有机合成中的应用

主要综述了近年来有机锰化合物及单质锰直接参与的有机反应有机合成中的应用。     

铟试剂在有机合成中的应用

综述了近十年来铟试剂在有机合成中的应用。重点讨论了铟试剂参与的有关碳-碳键形成的反应,如羰基化合物的烯丙基化、Reformatsky反应、成环以及三氯化铟作为Lewis酸的催化反应以及铟试剂的水相反应化学。铟试剂的这些反应,尤其是水相反应具有其它金属有机试剂在化学选择性和立体选择性方面具有独特的优势。     

Application of samarium reagents in organic synthesis

Application of samarium diiodide, samarium triiodide, Sm0/auxiliary system and organosamarium reagents in organic synthesis was reviewed.     

Colorimetric diffusion-reflection imaging high-throughput analysis of organic or inorganic compounds

A colorimetric diffusion-reflection imaging (CDRI) high-throughput analytical technology was developed for library analysis. In the investigation, quartz sands were employed as light diffusion-reflection media. Inorganic and organic compounds with characteristic absorption bands in visible light could be quantified by this method. In the current investigation, compounds such as CrCl3, KMnO4, methylene blue, and acrolein were employed as substrates, and the UV spectrometer and traditional GC (with thermal conductivity detector) were employed to check the reliability of our CDRI technology. The current technology is capable of analyzing more then 100 samples simultaneously. Relative errors below 10% were achieved.     

Infrared analysis of thin inorganic and organic films on metals

Infrared spectroscopy is shown to be an adequate method for qualitative and quantitative characterization of technical surface layers for corrosion protection. The measuring conditions for each type of sample have to be selected carefully. For the sake of reliability a certain redundancy in the evaluated data might be useful. It is the aim of this work to gather experience for routine quality control of steel and aluminium surfaces.Duridine, Granodine and Alodine used in this work are registered trademarks of Collardin GmbH