Determination of germanium after extraction by methyl isobutyl ketone. II

Summary Germanium extracted by methyl isobutyl ketone from 7.5N hydrochloric acid solutions is made to react directly in the organic phase with phenylfluorone. Very stable colored solutions are obtained. The reaction is instantaneous and twice as sensitive as when carried out in aqueous medium with the same reagent. Optimum range of concentration for absorptiometric measurements was found to be 0.08 to 0.30g Ge/ml. Most of the interfering ions are separated by preliminary extraction of the cupferrates with the same ketone. W(VI) and Nb(V) are removed by previous extraction with excess thiocyanate in reducing medium making use of the same solvent. The procedure is applicable to the determination of germanium in coals.

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Zusammenfassung Germanium wird aus 7,5-n Salzsäure mit Methylisobutylketon extrahiert und unmittelbar in der organischen Phase mit Phenylfluoron umgesetzt. Die Reaktion erfolgt sofort, ist doppelt so empfindlich als in wäßriger Phase und führt zu sehr stabil gefärbten Lösungen. Die für Absorptionsmessungen am besten geeignete Konzentration liegt zwischen 0,08 und 0,30g Ge/ml. Die meisten störenden Ionen werden durch vorhergehende Extraktion ihrer Cupferonate mit demselben Keton entfernt. Wolfram(VI) und Niob(V) werden mit demselben Lösungsmittel in Gegenwart überschüssigen Rhodanids in reduzierendem Milieu abgetrennt. Das Verfahren eignet sich für die Bestimmung von Germanium in Kohle.

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Résumé On fait réagir directement le germanium avec la phénylfluorone, dans la phase organique, après son extraction par la méthylisobutylcétone de sa solution 7,5N chlorhydrique. On obtient ainsi des solutions colorées très stables. La réaction est instantanée et deux fois plus sensible que lorsqu'elle est effectuée en milieu aqueux avec le même réactif. Le domaine de concentration optimum pour les mesures absorptiométriques est situé entre 0,08 et 0,30g Ge/ml. La plupart des ions gênants sont séparés par une extraction préalable des cupferrates par la cétone. W(VI) et Nb(V) sont éliminés au cours d'une extraction préalable en présence d'un excès de thiocyanate en milieu réducteur et dans le même solvant. La technique est applicable à la détermination du germanium dans les charbons.

     

Michael reaction,VI. Effect of carbonyl compounds on the stereochemistry and mechanism of the reaction

Zusammenfassung Die Stereochemie einer zweistufigen Gleichgewichts-Michael-Reaktion zwischen Dialkylamiden der Phenylessigsäure und Methylestern oder Dialkylamiden der Zimtsäure wird von den neutralen Carbonylverbindungen stark beeinflußt. Dieser Effekt kann mit der Zerstörung einer intramolekularen Chelatstruktur des Addukts und der darauffolgenden Bildung einer offenen Metallform mit einem dem neutralen Addukt ähnlichenerythro-threo-Verhältnis erklärt werden. Die Zunahme der elektrischen Leitfähigkeit des Reaktionsgemisches stützt diese Vorstellung.Es wird ein über das Chelat verlaufender Mechanismus im nichtpolaren Medium postuliert. Dieser Mechanismus ist in guter Übereinstimmung sowohl mit der geringen Stereoselektivität (bei kinetischer Kontrolle) als auch mit dem Einfluß der Lösungsmittel auf die Stereochemie.

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Michael reaction, VI. Effect of carbonyl compounds on the stereochemistry and mechanism of the reaction

The equilibrium stereochemical result of the two-stepMichael reaction between phenylacetic acid dialkylamides and methyl cinnamate or cinnamic acid dialkylamides is affected by the neutral carbonyl compounds taking part in the synthesis. This effect is explained by breakdown of the intramolecular chelate structure of the reaction adduct and appearance of an open metal form with isomeric partitioning close to that of the neutral adduct. This is further supported by the increased electroconductivity of the reaction mixtures. A chelate mechanism for the reaction in nonpolar medium is postulated which is in good agreement with the low stereoselectivity under kinetic conditions as well as with the effect of the polarity of the solvent on the kinetic stereochemical result.

     

Quantification of the Effect of an Impurity Addition on the Interaction Between Unlike Molecules in Mixed Liquids: A Theoretical Study

Journal of Solution Chemistry - The aim of this work is to develop a simple theory to study the effect of the addition of an impurity on the interaction between unlike molecules in mixed liquids....     

Production of color centers in PMMA by ultrashort laser pulses

We report here the creation of color centers in commercial, transparent PMMA samples by ultrashort pulses from a Ti:Sapphire laser emitting at 800 nm, with spatial control. Although the 800 nm photon energy is not sufficient to ionize the polymer, the centers are created following a multiphotonic absorption that causes the ionization. We propose that the free electrons quivering motion on the pulse electric field displaces atoms from its equilibrium positions, creating free radicals and double bonds that coalesce into color centers. The absorption and emission spectra of the centers were measured, but a dose-like curve could not be built due to the presence of damages created along with the centers that scatter the excitation and emission lights due to the commercial sample's poor optical quality.     

Three-dimensional MgB2-type superconductivity in hole-doped diamond

We substantiate by numerical and analytical calculations that the recently discovered superconductivity below 4 K in 3% boron-doped diamond is caused by electron-phonon coupling of the same type as in MgB2, albeit in three dimensions. Holes at the top of the zone-centered, degenerate sigma-bonding valence-band couple strongly to the optical bond-stretching modes. The increase from two to three dimensions reduces the mode softening crucial for T(c) reaching 40 K in MgB2. Even if diamond had the same bare coupling constant as MgB2, which could be achieved with 10% doping, T(c) would be only 25 K. Superconductivity above 1 K in Si (Ge) requires hole doping beyond 5% (10%).     

A Three-Dimensional Porous Organic Semiconductor Based on Fully sp2-Hybridized Graphitic Polymer

Dimensionality plays an important role in the charge transport properties of organic semiconductors. Although three-dimensional semiconductors, such as Si, are common in inorganic materials, imparting electrical conductivity to covalent three-dimensional organic polymers is challenging. Now, the synthesis of a three-dimensional π-conjugated porous organic polymer (3D p-POP) using catalyst-free Diels–Alder cycloaddition polymerization followed by acid-promoted aromatization is presented. With a surface area of 801 m² g⁻¹, full conjugation throughout the carbon backbone, and an electrical conductivity of 6(2)×10⁻⁴ S cm⁻¹ upon treatment with I₂ vapor, the 3D p-POP is the first member of a new class of permanently porous 3D organic semiconductors.     

Microbial and enzymatic hydrolysis of tannic acid: influence of substrate chemical quality

Tannic acid is commonly employed as the main component in culture media for the selection of tannase-producing strains. In biotechnological processes it is the favorite substrate used to induce the tannase enzyme in both solid and submerged culture for microbial and/or enzymatic production of gallic acid. However, the results found in literature are inconsistent notwithstanding the strict control of all parameters that rule the bioprocesses. The present work, for the first time, reveals the importance of differences in the quality and chemical profile of tannic acid from different suppliers and their influence on the fungal and enzymatic hydrolytic pattern obtained when it is used as a substrate. A degree of hydrolysis between 64.7 % and 100 % has been determined in different tannic acid samples. The specific growth rate of 0.712 h^?1, 0.792 h^?1, 0.477 h^?1, 0.536 h^?1 for Jalmek®, Faga Lab®, Division Food®, and Riedel de Häen®, respectively, was obtained at the concentration of 80 g L^?1 of each of the tannic acids.     

ACTION DES HYDRAZINES ET DE L'HYDROXYLAMINE SUR QUELQUES PHOSPHONATES β, β-BIFONCTIONNALISES: SYNTHESE DE PHOSPHONOAMINOPYRAZOLES ET ISOXAZOLES

Abstract

Reaction of hydrazines and hydroxylamine with β, β-bifunctionalized phosphonates 1 and 1′ leads to phosphoaminopyrazoles and isoxazoles 2 3, 4 and 5. The structure of all obtained products was confirmed by NMR and IR spectroscopy.     

Application of Fluorescence to the Study of Crude Petroleum

Crude petroleum oils are complex mixtures of different compounds (mainly organic), which are obtained from an extensive range of different geological sources. The fluorescence of crude petroleum oils derives largely from the aromatic hydrocarbon fraction, and this fluorescence emission is strongly influenced by the chemical composition (e.g., fluorophore and quencher concentrations) and physical characteristics (e.g., viscosity and optical density) of the oil. The fluorescence spectroscopy (FS) is increasingly used in petroleum technology due the availability of better optical detection techniques, because FS offers high sensitivity, good diagnostic potential, and relatively simple instrumentation. In this work we analyzed crude petroleum at different dilution in Nujol, a transparent mineral oil. The main objective of this work was to verify the possibility to measure crude oil emission spectroscopic without use of volatile solvents. The mixtures of nujol with different -crude oil concentrations were measured with a 10 mm optical path cuvette thus simplifying the fluorescence spectroscopy signal detection. The emission spectra were obtained by exciting the samples with a 400 W Xenon lamp at 350 nm, 450 nm and 532 nm. The emissions of the samples were collected perpendicularly with the excitation axis.