Mise au point de la chromatographie et du dosage du tungstène

Summary The chromatographic separation and determination of tungsten has been considered in the cases in which it occurs alone in solution or accompanied by chromium, vanadium, molybdenum, and iron. Two different types of chromatographic tests have been studied: usual partition chromatography and tests according to conditions B (different solvents for saturation, development, and contamination). To achieve a precise determination of tungsten and the absence of all interference, the usual partition chromatography must be adopted. The reproducibility of the determination of tungsten in this case is of the order of ±2 to 3% for 10g of the separated element. Under the conditions of the test B, the reproducibility of the determination of separated tungsten may be just as good (±3 to 4%) if use is made of conventional references and corresponding diagrams such as we recommend. Otherwise, the stains determined in the usual manner yield a deficit of 14% with respect to the deposited tungsten. In this study, the interfering factors play a predominant role from both the quantitative and qualitative points of view. This is the first time that we have been able to accomplish the determination of individual stains of chromatographed elements, remaining on the spot, of which a portion has been dispersed in the paper during the development. The chromatogram obtained under the separating conditions is much less beautiful since it leads to the migration of only the iron and the molybdenum, but it is this which is recommended to produce a perfect determination of tungsten. In the two cases of chromatography, the excess iron is separated from the tungsten during the development.

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Zusammenfassung Die chromatographische Trennung und Bestimmung von Wolfram in reinen Lösungen und in Gegenwart von Chrom, Vanadium, Molybdän und Eisen wurde untersucht. Hierzu wurden zwei verschiedene chromatographische Verfahren angewendet: die übliche Verteilung und eine Methode unter Anwendung verschiedener Lösungsmittel zur Sättigung, zur Entwicklung und als Zusatzmittel. Um eine genaue und störungsfreie Wolframbestimmung auszuführen, muß man die übliche Verteilungschromatographie anwenden. In diesem Falle ist die Reproduzierbarkeit der Wolframbestimmung in der Größenordnung von ±2 bis 3% für 10g des abgetrennten Elements. Bei Anwendung der zweiten Methode kann die Reproduzierbarkeit ebenfalls gut sein (± 3 bis 4%), wenn man sich eines geeigneten Standards und entsprechender, von uns empfohlener Diagramme bedient. Andernfalls ergeben die nach der üblichen Art bestimmten Chromatogrammflecken ein Defizit von 14% gegenüber dem angewandten Wolfram. Störungsfaktoren spielen hier eine vorherrschende Rolle, sowohl in qualitativer wie in quantitativer Hinsicht. Erstmalig hatten wir in diesem Falle an der Auftragstelle verbliebene Flecken eines Elementes zu bestimmen, von dem ein Teil während der Entwicklung sich auf dem Papier verteilt hatte. Das nach der üblichen Verteilungschromatographie erhaltene Chromatogramm ist zwar viel weniger schön, da nur das Eisen und das Molybdän wandern. Für eine perfekte Wolframbestimmung ist es aber zu empfehlen. Überschüssiges Eisen wird in beiden Fällen durch die chromatographische Entwicklung vom Wolfram abgetrennt.

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Les techniciensG. Wantier etA. Orban ont participé aux expériences.     

Synthese de derives mono- et bicycliques du bore tetracoordonne et des α-aminodiacides

Triethyl- and triphenyl-boranes react with α-aminodiacids, R¹N(CHR²COOH)₂ (R¹ = H, Me, PhCH₂; R₂ = H, Me), leading to mono- and bi-cyclic compounds. Depending on the experimental conditions and the substitution of the aminodiacid, either can be isolated. Eight compounds were prepared.     

La séparation et le dosage du tungstène et du molybdène au moyen du chlorure de calcium

A rapid and simple method is described for the separation and the determination of molybdenum and tungsten. Both metals are extracted as their soluble salts, sodium molybdate and sodium tungstate, by means of an alkaline fusion (Na₂CO₃ + Na₂O₂), after which they are separated by precipitation with calcium chloride as reagent. The precipitates of calcium molybdate and calcium tungstate are filtered, washed and then decomposed by concentrated hydrochloric acid. Calcium molybdate passes completely into the filtrate while calcium tungstate leaves a precipitate of tungstic acid. By calcining this precipitate, tungstic trioxide is obtained and weighed. The tungsten content is calculated therefrom.The filtrate from tungstic acid serves for reprecipitation of calcium molybdate on making the solution alkaline and by boiling. Calcium molybdate is filtered by means of a porcelain crucible filter and then calcined. When the weight of the calcined precipitate is constant, the molybdenum content is obtained by multiplying the weight of the precipitate by the conversion factor. Results are satisfactory, separation and determination of both metals not taking more than a day's work.     

Intercalation dans le graphite du sulfure et du séléniure de potassium

The reaction between graphite and liquid potassium, containing small amounts of sulphur or selenium, leads to the synthesis of new lamellar compounds, of which the three-layered intercalated sheets can be regarded as potassium sulfide or selenide slices, being arranged between the graphene planes. These slices retain the hexagonal symmetry that they possess in the 3D binary chalcogenides, thanks to some adaptations. Particularly, they become commensurate with respect to the graphene planes.     

La séparation du scandium,du lanthane et de l'yttrium

The behaviour of scandium on a resin column has been studied and an efficient separation of scandium, lanthanum and yttrium has been effected using citric acid at different pH's. The hysteresis phenomenon which accompanies the adsorption of scandium and its importance for calculations, based on the theory of levels, are discussed.     

Viscoplasticité dynamique du polycarbonate: Influence de la vitesse de sollicitation et des traitements de recuit

The present paper deals with the study of engineering polycarbonates, investigated at high compressive strain rates (1100–3200 sec⁻¹), by means of Hopkinson pressure bar apparatus. Special attention was devoted to the influence of thermal pre-treatment and the viscoelastic behaviour in the glassy state. The results are compared to those obtained at low strain rates (10⁻²−1 sec⁻¹).     

Synthèse de nouveaux dérivés du 1-hydroxyindole et du pyrazole

New 1-hydroxyindole derivatives have been synthesised by alkylation, acylation reactions and by condensation with acetylacetone and dehydroacetic acid. Action of hydrazines on 3-acetyl-1-hydroxy-indole leads to new pyrazole derivatives.     

Macrocyclisation en series lactone,thiolactone et lactame à motif ethylenedioxy: Effets de matrice du siliceum et de l'etain

The orientation of the macrocyclizacion reaction leading to the di or tetrafunctional titled compounds has been studied for 12 and 24 membered rings containing ethylene dioxy moieties. The reactions were carried out from not activated diol, dithiol or diamine and from their silyl and stannyl derivatives. They were not performed at high dilution. The intracyclic oxygen atoms had a strong influence on the orientation of the cyclisation towards the monomer. However, it was also possible to obtain the dimeric forms with yields ranging from 10 to 40%.     

Synthèse domino du noyau tricyclique ABC de strigolactones et analogues

The diversity-oriented synthesis of the ABC tricyclic core of strigolactones and analogues is described starting from ortho-halogenated aromatic or vinylic carbonyl compounds and dimethyl itaconate. It involves a conjugate addition/aldol coupling/lactonization domino process that allows the formation of three carbon–carbon bonds in a single experimental step. Functional group interconversions as well as a putative reaction mechanism are presented.     

Conductivité hydraulique et progression du front de dessiccation dans une argilite

The “Schistes carton” formation is highly overconsolidated and hardened in its intact form. The variations of hydraulic and/or mechanical stresses on this material lead to an alteration as well as a change in its mechanical properties. Experiments have been carried out to study the advancement of the desiccation front and the hydraulic conductivity of this unsaturated soil. The samples are from Pont-à-Mousson Lorraine. The evolution of the volumetric water content versus the depth and the variations of the hydraulic conductivity have permitted the estimation of the alteration depth in this formation.     

Identification du mercure-I,du mercure-II et du molybdène

Résumé Dans le présent travail, on expose les réactions concernant l'identification de Hg-I, Hg-II et du Mo. Ces réactions sont basées sur la réduction de MoO₄ ^2– par Hg élémentaire en milieu d'acide chlorhydrique. Il en résulte une coloration bleue et une coloration rouge. Ces réactions sont spécifiques et elles peuvent être utilisées dans l'analyse des substances contenant ces éléments.

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Summary This study deals with reactions serving for the identification of Hg(I), Hg(II), and Mo. These reactions are based on the reduction of MoO₄ ^2– by elementary mercury in a hydrochloric acid medium. A blue coloration results and also a red coloration. These reactions are specific and they may be employed in the analysis of samples containing these elements.

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Zusammenfassung In der vorliegenden Arbeit werden Tüpfelreaktionen zur Bestimmung von Quecksilber(I), Quecksilber(II) und Molybdän vorgeschlagen. Diese Reaktionen beruhen auf der Reduktion von Molybdat durch elementares Quecksilber in salzsaurem Medium. Dabei entsteht eine blaue und eine rote Färbung. Die Reaktionen sind spezifisch und allgemein anwendbar.

     

Spectres de vibration et liaison hydrogène du cyclobutane 1-1 dicarboxylate acide de potassium

The crystal structure of potassium hydrogen cyclobutane 1-1 dicarboxylate has been determined by X-ray analysis. This acid salt has a short unsymmetrical intermolecular hydrogen bond with O … O = 2,53 Å, but the carboxylic residues show only small differences in dimensions. Polycrystalline samples of CB(COO)₂HK-1,1 and its O-deuterated analog have been studied by i.r. and Raman spectroscopy. An assignment of the bands is given, the details of the hydrogen bond bands are discussed; in particular the isotopic ettect (νOH/ νOD ∼ 1), the combination bands in the region 1900–2500 cm⁻¹ and the carbonyl region. It suggested that the acid salt belongs to Speakman's pseudo A type.     

Separation et dosage de traces de bore dans le silicium : Nouvelle méthode de séparation et de dosage de traces de bore. application au dosage du bore dans le silicium

A new method is described for the separation and determination of traces of boron by extraction of methylene blue fluoroborate by dichlorethane The method has been applied to the determination of traces of boron in silicon and silica     

Détermination des cinétiques de croissance et de dissolution du perborate de sodium tetrahydrate en lit fluidisé

The authors present the results of an experimental study on the crystallization of tetrahydrate sodium perborate in a fluidized bed. The influences of supersaturation, seed crystal size, temperature and solution velocity on the overall growth rate were examined. The overall dissolution rate determined under comparable hydrodynamical conditions for various seed crystal sizes and temperatures is also reported.The growth rate is not very sensitive to the variations in crystal size, the temperature and the hydrodynamical conditions, but it depends on the supersaturation and the presence of some soluble impurities.The comparison between growth and dissolution rates shows that under actual working conditions the diffusional mass transfer step is not the limiting step of the growth mechanism.     

Détermination spectrale du phosphore et du carbone dans les aciers par la méthode de profilage

Sans résuméLes recherches ont été effectués sous les auspices de l'I. R. S. I. A. (Institut pour l'encouragement de la Recherche Scientifique dans l'Industrie et l'Agriculture) et du C. N. R. M. (Centre National des Recherches Métallurgiques) Section Hainaut.     

Étude du dosage du phosphore et de l'arsenic dans les aciers par colorimétrie

Phosphomolybdic and arsenomolybdic acids are formed and reduced to their blue reduction products at normal temperature in the presence of certain metallic ions: bismuth, zirconium, titanium. Of these ions, the last two catalyse the reduction of molybdic acid under acid conditions favourable to the reduction of phospho- and arsenomolybdic acids. Bismuth does not bring about this last reaction. It was chosen because of its analytical applications, which are related to the estimation of phosphorus and arsenic in steels. The working methods proposed are given in an appendix.     

Dosage de l'histidine: Étude polarographique et dosage du dinitrofluorobenzene

After polarographic study and determination of dinitrofluorobenzene at varying pH and determination of a number of electron exchanges (n), standardization curves have been constructed at pH 5 and 10. They allow the estimation of DNFB to a concentration of 1γ/ml with a precision of 4–7%. The curve shows 2 or 3 leaps, according to pH.. The E_{$\text{1}\text{2}$} of the first two are less than 1 volt.     

Sur une nouvelle réaction colorée du cuivre et de l'urobiline

Résumé L'urobiline permet de déceler et même de doser colorimétriquement de très petites quantités de cuivre dissoutes dans l'eau, même en présence de métaux étrangers. La coloration est rose autour de la teneur du millionième et déjà purpurine à la teneur du centmillième. La réaction est des plus sensibles car elle se produit encore lorsqu'il n'y a qu'un dix millième de milligramme du métal dans un centimètre cube de solution. Inversement, les sels de cuivre peuvent servir comme réactif de l'urobiline.

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Summary With the help of urobilin it is possible to detect and to determine, by a colorimetric method, very small amounts of copper in aqueous solution, in the presence of other metals. The reaction-colour is pink at a dilution of 1:1 000 000 and turns to purple at a dilution of 1:100 000. The reaction being very sensitive it is possible to detect 0,0001 mg of copper in 1 ccm of the solution tested. On the other hand, copper salts can be used for the detection of urobilin.

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Zusammenfassung Mit Urobilin lassen sich sehr kleine Mengen von Kupfer in Wasser gelöst nachweisen und kolorimetrisch bestimmen, und zwar auch bei Anwesenheit anderer Metalle. Die Reaktionsfärbung ist rosa bei einer Verdünnung von etwa 1:1 000 000 und schon purpurfarbig bei einer Verdünnung von 1:100 000. Die Reaktion zeichnet sich durch hohe Empfindlichkeit aus, denn noch in 1 ccm einer Lösung von 0,0001 mg des Metalles ist sie positiv. Umgekehrt können Kupfersalze als Reagens für Urobilin dienen.

     

La détermination rapide du calcium et du magnésium dans l'eau de mer

A rapid method is described for the determination of calcium and magnesium in sea. water. The classical gravimetric methods are very lengthy and are susceptible to errors if used for sea-water. The two alkaline earths are determined by complexometric titration using complexen III (disodium ethylenediaminetetra-acetate) as reagent and two indicators (murexide and ériochrome black T) for the determination of calcium and for the sum of Ca⁺² and Mg⁺² ions. The quantity of magnesium is obtained by difference. While the classical gravimetric methods take at least 24 hours, these two determinations can be effected in 1 hour, giving satisfactory accuracy.