Lanthanum-based perovskites obtained in molten nitrates or nitrites

Lanthanum-based perovskites, LaMO₃ (where M = Mn, Fe, Co, Ni), have been synthesised from lanthanum precursors and corresponding 3d transition metal salts in molten alkali metal nitrates or nitrites. The reactivity of eight precursors in three molten salts of different basicity was analysed. Single phase orthorhombic LaMnO_3.11, and orthorhombic LaFeO₃ have been obtained in molten NaNO₂ at 723 K, for 2 h. LaCoO₃ is also formed in molten nitrite, but an increase of basicity, by adding Na₂O₂, was necessary to obtain LaNiO₃. The reaction systems were investigated by thermal analysis. X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and specific surface area measurements (BET method) were used to characterise the synthesised nanopowders.     

A modification of the heteropoly blue method for the microgram determination of arsenic in biological materials

Summary A sensitive method has been developed for analysis of trace amounts of arsenic in biological materials using the heteropoly blue method. The method employs a closed apparatus and a nitrogen atmosphere, and allows the detection of arsenic in ppm concentration using samples of 100 mg.

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Zusammenfassung Eine empfindliche Methode zur Bestimmung von Arsenspuren in biologischem Material im Wege der Molybdänblaumethode wurde ausgearbeitet. Man arbeitet dabei in einer geschlossenen Apparatur in Stickstoffatmosphäre und kann so in 100-mg-Proben Arsenkonzentrationen in der Größenordnung von ppm bestimmen.

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Presented at the 6th Annual Northeast Regional Meeting of the American Chemical Society, Burlington, Vermont, August 19, 1974.     

The solvent extraction of Cu(II), Ni(II), and Co(II) with diacetyl-mono-(2-quinolylhydrazone)

Summary A semi-automatic microliter sample injector with an 8-way motor-driven rotary valve was constructed for a conventional pneumatic nebulizer. After a 40-l sample was injected into an injection tee with a micro-syringe, nebulization and flushing the sample pathway with water followed by argon were automatically executed. An automatic peak detector/integrator was employed in each channel of a three-channel spectrometer for simultaneous multielement analysis. The relative standard deviation of the peak height for 1g Zr/ml was 1.7% and measuring time of one sample was about 1 min. Detection limits were 2 to 6 times higher than those in continuous feeding.

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Halbautomatische Injektion von Mikroliter-Proben in ein induktiv gekoppeltes Plasma zwecks simultaner Multielementanalyse

Zusammenfassung Ein halbautomatischer Injektor für Mikroliterproben mit einem motorgetriebenen 8-Weg-Ventil für ein konventionelles Vernebelungsgerät wurde konstruiert. Nachdem eine 40-l-Probe mit einer Mikroinjektionsspritze in ein Injektions-T-Stück eingeführt ist, erfolgt automatisch Vernebelung, dann Spülung des Probenweges zunächst mit Wasser, dann mit Argon. Ein automatischer Spitzen-Detektor/Integrator in jedem der drei Kanäle des Spektrometers ermöglicht die gleichzeitige Multielementanalyse. Die rel. Standardabweichung der Spitzenhöhe für 1g Zr/ml betrug 1,7%, die Zeit für die Messung einer Probe ungefähr eine Minute. Die Nachweisgrenzen sind 2- bis 6mal höher als bei kontinuierlicher Zugabe.

     

Organically modified sols as pseudostationary phases for microchip electrophoresis

We demonstrate that the selectivity of microchip electrophoresis separations is greatly improved by the presence of organically modified silica (Ormosil) sols in the run buffer. A negatively-charged N-(trimethoxysilylpropyl)ethylenediamine triacetic-acid (TETT)-based sol is used for improving the selectivity between nitroaromatic explosives and a methyltrimethoxysilane (MTMOS)-based sol is employed for enhancing the microchip separation of environmental pollutants, aminophenols. These sols are added to the run buffer and act as pseudostationary phases. Their presence in the run buffer changes the apparent mobility of studied solutes, and leads to a higher resolution. The observed mobilities changes reflect the interactions between the Ormosil sols and the solutes. Relevant experimental variables have been characterized and optimized. The diverse chemistry of Ormosil sols should be extremely useful for tailoring the selectivity of a wide range of electrophoresis microchip separations.     

Diacetyl-bis-(2-pyridyl)hydrazone as an extracting agent for Cu(II), Co(II), and Ni(II)

Summary DbPH, a quadridentate chelating agent, was studied as a solvent extraction reagent for Cu(II), Co(II), and Ni(II). In all cases 11 complexes were extracted; however for Cu(II) and Co(II) ion-paired species exist, while for Ni(II) only neutral complexes were extracted. In all cases an extraction efficiency of 35–60% was observed unlike the greater than 90% observed for similar mono-hydrazone derivatives. The steric hindrance probably present in the bis adduct prevented a more efficient extraction.

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Diacetyl-bis-(2-pyridyl)hydrazon (DbPH) als Extraktionsmittel für Cu(ll), Co(II) und Ni(II)

Zusammenfassung DbPH bildet mit Cu(II), Co(II) und Ni(II) Komplexverbindungen im Verhältnis 11; diese sind für Cu und Co ionisierbar, im Falle des Ni läßt sich ein neutraler Komplex extrahieren. Die Extraktion erreicht jedenfalls nur 35–60% im Gegensatz zu mehr als 90% bei ähnlich gebauten Monohydrazon-Derivaten. Sterische Hinderung dürfte hierfür die Ursache sein.

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Presented at the 18th Middle Atlantic Regional Meeting of the American Chemical Society, Newark, New Jersey, May 21, 1984.     

Matrix-isolation-FTIR spectroscopy with an integrating sphere

The use of an integrating sphere for the measurement of absorption spectra of thin films is described. The thin film (for example a rare gas matrix) is grown directly on the inside surface of the sphere. Multiple reflections inside the integrating sphere lead to significant enhancement of weak absorptions of the film, increasing the sensitivity of such measurements.     

Amide interactions in chlorinated solvents

Enthalpies of solution and of transfer of amides for the solvents chloroform (CHCl₃), methylenechloride (CH₂Cl₂), carbontetrachloride (CCl₄), cyclohexane (C₆H₁₂), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA), and ethylacetate (EtOAc) have been used to isolate and quantify the solvation interactions of amides in chlorinated solvents. Specific interactions at the aminde carbonyl and N–H groups have been identified. An analysis of the transfer enthalpies of pyrrole and methylpyrrole from cyclohexane to the chlorinated solvents shows that specific interactions between the pyrroles and these solvents are similar in nature. A means of calculating differences in the transfers of different solutes between the same solvent pair is given.Work done at Lebanon Valley College.     

Aromatisierung von cytclohexenon-derivaten über selenorganische zwischenstufen

Reaction of the hydroaromatic compounds ($\text{1a}$) and ($\text{3a}$) with lithium-diisopropylamide followed by phenylselenenyl chloride gives the selenides ($\text{1b}$) and ($\text{1c}$) resp. ($\text{3b}$), which form exclusively the phenols ($\text{4}$) resp. ($\text{6}$) after oxidation with 3-chloroperbenzoic acid in the presence of 3,5-dimethoxyaniline ($\text{7a}$).     

Pure and doped lanthanum cobaltites obtained by combustion method

We report the synthesis of La_1−xSr_xCoO₃ nanopowders by solution combustion method using metal nitrates and -alanine (alanine method) or urea (urea method) as fuel. The influence of metal nitrates/organic substance molar ratio and the type of fuel was investigated. The isolated complex precursors were characterized by atomic absorption spectroscopy (AAS), FT-IR spectra and DTA–TG analysis. The La_1−xSr_xCoO₃ (x = 0–0.3) powders were characterized by X-ray diffraction (XRD), scanning electron microscopy–energy-dispersive X-ray analysis (SEM–EDX), as well as by specific surface area measurements. XRD patterns indicate the formation of single-phase LaCoO₃ (rhombohedral) when as-synthesized powders were calcined at 873 K, 3 h in the case of the alanine method and at 1073 K, 3 h for urea-based system. Also, strontium doped lanthanum cobaltites obtained by both methods at 1273 K are single phase with rhombohedral perovskite-like structure as XRD data have proved. SEM investigation of pure and doped lanthanum cobaltites reveal that the samples prepared by both methods have fine particles with tendency of agglomerates formation with different shapes, spongy aspect and high porosity. La_1−xSr_xCoO₃ nanopowders obtained by alanine method have larger specific surface area values than those prepared by urea method.