Solid state reactivity of organic compounds with inorganic compounds. IV synthesis and thermal decomposition of uranium oxinate in the solid state

8-hydroxyquinoline (oxine) and uranyl acetate react in the solid state in 13 stoichiometry to give UO₂(C₉H₆NO)₂·C₉H₆NOH. This reaction is diffusion controlled with an activation energy of 44.4 kJ mol^–1. The reaction occurs by the surface migration of 8-hydroxyquinoline, which penetrates the product lattice to react with uranyl acetate. The isothermal decomposition of the solution phase product UO₂Q₂·HQ (Q=C₉H₆NO) obeys the Prout-Tompkins equation with an energy of activation of 53.3 kJ mol^–1.

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Zusammenfassung Die Festkörperreaktion von 8-Hydroxychinolin und Uranylazetat im Verhältnis 13 liefert UO₂(G₉H₆NO)₂·C₉H₆NOH. Die Reaktion ist diffusionsbestimmt und besitzt eine Aktivierungsenergie von 44.4 kJmol^–1. Die Reaktion verläuft durch die Oberflächenmigration von 8-Hydroxychinolin, welches zur Reaktion mit Uranylazetat in das Gitter des Produktes eindringt. Die thermische Zersetzung der Mischphase UO₂Q₂·HQ mitQ=C₉H₆NO unterliegt der Prout-Tompkins-Gleichung mit einer Aktivierungsenergie von 53,3 kJ·mol^–1.

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8- 13, UO₂(C₉H₆NO)₂·C₉H₆NOH. 44,4 ·^–1. 8-, . UO₂ Q ₂ · HQ (Q=C₉H₆NO) - 53,3 ·^–1.

     

Solid state reactions of nitrogenous heterocyclic compounds (II)

Solid state Michael addition reaction of indole with α, β-unsaturated carbonyl compounds was carried out, by which a series of compounds containing three different heterocyclic groups binding to one carbon atom were ob-tained. In the presence of Lewis acid, indole could undergo the solid state condensation reaction with aromatic ketones and aldehydes or quinones. The solid state reaction showed higher selectivity and yield than solution reaction. The structures of products were identified by IR,¹H NMR, MS. elemental analysis and X-ray crystal analysis. The reac-tion mechanism was also proposed. Project supported by the National Natural Science Foundation of China     

On the reactivity of recoil tritium with organic compounds

The reactivity of recoil tritium in the T-for-H substitution was studied in mixtures of benzene, hexane, cyclohexane or cyclohexane-d₁₂ with lithium carbonate which were irradiated in a reactor. The relative rates per C–H bond of hexane and cyclohexane to benzene were somewhat less than one third. The H/D isotope effect in cyclohexane was given as 1.14.     

Solid state chemical ionization for characterization of organic compounds by laser mass spectrometry

A new technique involving the addition of a compound to the analyte to serve as a source of "reagent" ions has been developed for negative-ion laser mass spectrometry. This "solid state chemical ionization" leads to ions characteristic of the analyte, owing to ion-molecule reactions between the "reagent" ion and the neutral analyte in the laser-generated plume. Polycyclic aromatic hydrocarbons show formation of an ion corresponding to (M + O - H)(-) in their negative-ion laser mass spectra when mixed with compounds such as sym-trinitrobenzene, sodium nitrate and sodium peroxide. NO(-)(2), O(-), and O(-)(2) serve as "reagent" ions in these compounds. Formation of (M + Cl)(-) is seen in the laser mass spectra of glycosides mixed with hexachlorobenzene. Chloride serves as the "reagent" ion in this case.     

Solid state photoreactions occurring at the interface between crystallites of two different organic compounds

This paper deals with the solid state bimolecular photoreactions occurring at the interface between crystallites of two different organic compounds prepared as a polycrystalline mixture by melting-resolidification. The photoreactions include the photoaddition of NH compounds to aromatic and olefinic double bonds, hydrogen abstraction, condensation reaction via photoelectron transfer and [2+2] photoaddition. Particular attention is focused on the characterization of the polycrystalline mixture, the selectivity of the photoreactions in the solid state compared with those in the solution phase and the factors controlling the photoreactions.     

Solid state reactivity and mechanisms in oxide systems

Starting from oxalate mixed crystals Ni_xMn_3?x(C₂O₄)₃·6H₂O thermal decomposition at reduced oxygen partial pressure (po₂= 2%) leads to the formation of NiMn₂O₄ (x = 1) at metastable conditions. Ni_1.5Mn_1.5O₄ (x = 1.5) existing in the metastable state only has been also prepared. The spinel compounds both are of the highly inversed type. Following a sol-gel preparation route Mg₂TiO₄ has been also found to be formed in the metastable state. Annealing results in decomposition of the compounds providing NiMnO₃ and 1/2α-Mn₂O₃ or NiMnO₃ only or MgTiO₃ and MgO, respectively. The reaction rates observed are lower for NiMn₂O₄ and Ni_1.5Mn_1.5O₄ than for Mg₂TiO₄ decomposition. The reverse reaction of NiMn₂O₄ formation above 730°C shows an endothermic enthalpy of +61 kJ·mol^?1. For Mg₂TiO₄ formation above 1050°C an endothermic enthalpy of +19.3 kJ·mol^?1 is found. The results are discussed in terms of structural features of the oxides.     

含氮杂环化合物的固相光化学

本文研究了含氮杂环化合物同尿嘧啶醛、芳香醛酮、稠环化合物的固相光化学反应, 得到与液相光化学反应不同的结果。合成了十九种新化合物, 它们的结构由IR, ^1H NMR, MS和元素分析确定。用光谱方法表征了混晶的性质。X射线粉未衍射和差热分析表明, 吲哚同萘, 咔唑同蒽的混晶, 形成了分子化合物。对反应机理进行了初步探讨。     

Determination of the solubility of organic compounds. II

Summary In general, solid particles liquify when they are exposed to air laden with the vapor of a liquid in which they are soluble. There are exceptions, however, which may be explained by assuming the formation of a solvate.

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Zusammenfassung Feste Teilchen verflüssigen sich im allgemeinen, wenn sie Luft ausgesetzt sind, die mit dem Dampf einer Flüssigkeit geladen ist, in der sie löslich sind. Es wurden aber Ausnahmen gefunden, die möglicherweise durch die Bildung von Solvaten erklärt werden können.

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Résumé Généralement, les particules solides se liquéfient si elles sont exposées à l'air chargé de la vapeur d'un liquide dans lequel elles sont solubles. Il existe cependant des exceptions que l'on peut expliquer en supposant la formation de solvates.

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On the occasion of the hundredth return ofFriedrich Emich's birthday.

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The authors wish to express their appreciation to ProfessorO. F. Steinbach for his suggestions and advice.     

Capillary electrophoretic separation of inorganic and organic arsenic compounds

Capillary zone electrophoresis was used to separate arsenite, arsenate, dimethylarsinic and diphenylarsinic acid, methanearsonic acid, phenyl- and p-aminophenyl arsonic acid, phenylarsineoxide and phenarsazinic acid. Anionic and uncharged species were separated in a fused silica capillary with on-column UV detection at 200 nm. A 15 mM phosphate solution adjusted to pH 6.5 containing 10 mM sodium dodecylsulfonate served as background electrolyte. The influence of pH and applied voltage on separation efficiency, as well as the feasibility of identification of arsenic compounds in spiked urine, were investigated. Received: 18 March 1998 / Revised: 25 May 1998 / Accepted: 30 May 1998     

Ultramicro detection of iodine in inorganic and organic compounds

Zusammenfassung Die Redoxreaktion zwischen Chloramin T und dem Acetat der Tetra-base, die sehr langsam zu einer blauen wasserlöslichen p-chinoiden Verbindung führt, wird durch Jodionen katalytisch beschleunigt. Darauf läßt sich bei Einhaltung leicht realisierbarer Bedingungen ein Nachweis von Jod begründen, der eine Erfassungsgrenze von 0,0004 g in einem Tropfen und in 10 ml besitzt. Die entsprechenden Verdünnungsgrenzen sind 1 125000000 bzw. 1 25000000000.Der neue Nachweis ist anwendbar zur schnellen Prüfung auf Jod in Trink-, Mineral- und Meerwasser ohne vorherige Anreicherung durch Eindampfen. In organischen Verbindungen kann Jod eindeutig und mit mikroanalytischen Erfassungsgrenzen nachgewiesen werden.Es besteht begründete Aussicht auf eine Anwendung der Katalysenreaktion zur colorimetrischen Bestimmung minimaler Jodmengen.     

Capillary electrophoretic separation of inorganic and organic arsenic compounds

Capillary zone electrophoresis was used to separate arsenite, arsenate, dimethylarsinic and diphenylarsinic acid, methanearsonic acid, phenyl- and p-aminophenyl arsonic acid, phenylarsineoxide and phenarsazinic acid. Anionic and uncharged species were separated in a fused silica capillary with on-column UV detection at 200 nm. A 15 mM phosphate solution adjusted to pH 6.5 containing 10 mM sodium dodecylsulfonate served as background electrolyte. The influence of pH and applied voltage on separation efficiency, as well as the feasibility of identification of arsenic compounds in spiked urine, were investigated. Received: 18 March 1998 / Revised: 25 May 1998 / Accepted: 30 May 1998     

Kinetic determination of some inorganic and organic compounds by oxidation with iodate

Sulphite (5.0 × 10^?1?5.0 × 10^?3 M), ascorbic acid and other compounds are oxidized by potassium iodate in dilute sulphuric acid; the production of iodide is monitored by an iodide-selective electrode. The time needed for a 40-mV potential change is inversely proportional to concentration. For sulphite (1.0 × 10^?5?1.0 × 10^?4 M), selectivity is improved by sweeping the sulphur dioxide formed in acidic EDTA-containing solution into the iodate solution.     

Transformation of organic and inorganic compounds in trifluoroacetic acid

It is established that the effectiveness of fluorine-containing acids in the transformation of organic and inorganic substrates is due to the ability of the acid to perform several functions: to accumulate relatively high concentrations of molecular oxygen, to activate it, and to serve as a hydrogen-containing medium.     

Solid state reactions of nitrogenous heterocyclic compounds (I) —Solid state reactions of 3-methyl-1-phenyl-5-pyrazolone with carbonyl compounds

The solid state reaction of 3-methyl-1-phenyl-5-pyrazolon(eM PP) with aromatic aldehydes and ketones, benzil derivatives and imides, and the solid state Michael addition reaction of MPP with 4-arylidene-3-methyl-lphenyl-5-pyrazolone2 were investigated. Some new solid state reactions between the reactants were found, from which a series of new compounds were obtained. The structures of the products were identified by IR,¹H NMR, MS, elemental analyses and also by X-ray crystal analysis, and the reaction mechanism of MPP with aromatic aldehydes and ketones was proposed. Project supported by the National Natural Science Foundation of China.     

Identification and quantification of inorganic and organic selenium compounds with highperformance liquid chromatography

Selenium appears in the natural selenium cycle in the form of several organic and inorganic compounds. The biologically beneficial and deterimental effects of ‘selenium’ must be ascribed to particular selenium compounds. The identification and quantification of selenium compounds in biological and environmental samples is required for an understanding of the role of selenium. The high-performance liquid-chromatographic (HPLC) methods for the separation, identification and quantification of selenite, selenate, hydrogen selenide, methaneselenol, bis(organothio) selenides, trimethylselenonium salts, selenonamino-acids, selenium derivatives of carbohydrates, selenoproteins, selenonucleosides and other miscellaneous selenium compounds are summarized (193 references) and pertinent detection modes discussed. Advantages and disadvantages of the methods are pointed out. The literature is covered since 1974, the year of the first publication in this field.     

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.     

Utilization of inorganic and organic arsenic compounds in new technologies

This paper reviews the use of arsenic compounds in semiconductor manufacture and emphasizes the role of alkylated arsenic compounds.