The preparation,phase relationships,and Eu-151 Mössbauer spectroscopy of europium tungsten bronzes and related phases

Crystal chemistry and phase relations for the bronze-forming region of the EuWO system have been investigated. A bronze Eu_xWO₃ is stable up to 1000°C when x ? 0.125 and in the region 0.085 ? x ? 0.125 the symmetry is cubic. A tetragonal bronze exists at x = 0.05, and an orthorhombic bronze with a structure closely related to the orthorhombic form of WO₃ exists below x = 0.01. Mössbauer spectra at room temperature and at 80 K indicate that in all these phases the europium is highly ionized as Eu(III) with no electron localization to give (EuII) even at low values for x. The decomposition products of the bronzes have been established, and the Mössbauer parameters for the highly nonstoichiometric tungstates Eu_xWO₄ were determined. Both Eu(II) and Eu(III) resonances were obtained, and a cation vacancy model for Eu_xWO₄ was found to fit the data best. In conformity with the foregoing data, a sample of composition “Eu₂W₂O₇” was found not be be a pyrochlore but to comprise a mixture of Eu₆WO₁₂, Eu_xWO₄, and W. The phase relationships for the europium bronze system Eu_xWO₃ are compared with those of other ionic bronzes Na_xWO₃, Li_xWO₃, and Al_xWO₃.     

The polymorphic transformations of cobalt molybdate

Polymorphic transformations of CoMoO₄ were studied by means of high temperature X-ray measurements within the temperature range 25–1200°C. On heating phase a obtained from low temperature modification b a new modification a′ was discovered. Phase a obtained by thermal decomposition of solvated α-CoMoO₄ shows different behaviour. At 700–930°C depending on the conditions of preparation it transforms irreversibly into still another modification a″. On cooling, a mixture of phases a + a″ is obtained, the presence of a″ being responsible for the explosionwise transition into b, observed around the room temperature.     

Evaluation of a carbon-rod atomizer for routine determination of trace metals by atomic-absorption spectroscopy applications to analysis of lubricating oil and crude oil

A carbon-rod atomizer (CRA) fitted with a 'mini-Massmann' carbon rod was evaluated for routine analysis of petroleum and petroleum products for trace metal content by atomic-absorption spectroscopy. Aspects investigated included sensitivity, detection limit, effect of solvent type, and interferences. The results of analysis of oil samples with this technique were compared with those obtained by other techniques. Metals studied were silver, copper, iron, nickel, and lead. Sensitivity and detection limit values obtained with the CRA were similar to those obtained with the carbon-filament atomizer. Strong 'solvent effects' were observed as well as interference by cations. On the basis of this study, design changes for the CRA are suggested, with the object of minimizing 'solvent effects' and interferences, increasing the atomization efficiency, and increasing the residence time of the atomic vapour in the optical path of the instrumental system.     

Nitro compounds as alkylating reagents in friedel-crafts conditions : Reaction of 2-nitropropane with benzene

Friedel-Crafts reaction of benzylic or tertiary nitro compounds with benzene gave normal alkylation products. Similarly, 2-nitropropane (2-NP) gave cumene (1) which underwent further transformation affording a mixture whose behaviour with time was investigated : results were consistent with oxidative formation of the cumyl carbonium ion (7').     

Reaction of β-amino-α,β-unsaturated esters and amides with aryl diazonium salts : Synthesis of cinnoline derivatives

Conjugated esters and amides react with aryldiazonium salts at room temperature (MeCN) to form the corresponding iminium hydrazone derivatives, which can be thermally cyclized to cinnoline-3-esters and cinnoline-3-amides. In general the intermediate iminium salts derived from the enamine amides cyclize faster than those from the enamine esters. Furthermore, the ease of cyclization depends upon the structure of the base-component of the enamine ester or the amide and the substituent in the aryl moiety of the diazonium salt. The configurational structure of the iminium hydrazones, studied by NMR spectroscopy, has been shown to involve H-bonding of the hydrazonyl N-H with the ester or the amide CO group.     

Benzo[b] thiophene derivatives. XVIII. The sulfur isosteres of harmaline,harmine and related isomers

The sulfur analogs of harmaline, 7-methoxy-3,4-dihydro-1-methyl[1]benzothieno[2,3-c]-pyridine (Ib), harmine, 7-methoxy-1-methyl[1]benzothieno[2,3- c ]pyridine (IIb), and corresponding 6-methoxy isomers (Ic and IIc) have been synthesized for pharmacological evaluation as monoamine oxidase inhibitors.     

Bulk and localized oxygen concentration measurements of steam-oxidized zircaloy-4 using nuclear analysis techniques

Quantitative measurement of both bulk and localized oxygen concentrations is of importance in the study of oxidation kinetics. We describe the combined application of two nuclear techniques, fast neutron activation analysis and (d, p) nuclear microprobe, to the determination of oxygen concentrations and surface profiles for steam-oxidized Zircaloy-4 cladding specimens. Results of measurements using these techniques are presented. Work partially supported by Electric Power Research Institute Contract T.S.A. No. 20.     

Regiospecific α-dialkoxymethylation of preformed enolates

Reaction of a preformed lithium enolate and trimethyl orthoformate with added boron trifluoride leads to the corresponding α-dimethoxymethyl ketone.     

Fast formation of aromatic cations in cyclohexane observed by pulse radiolysis

The fast formation of cations of benzophenone, biphenyl, naphthalene, anthracene and phenanthrene in liquid cyclohexane was studied by nanosecond pulse radiolysis. Rate constants between 2.3 × 10¹⁰ M^?1 s^?1 (for naphthalene) and not below 2.5 × 10¹² M^?1 s^?1 (for benzophenone) were derived and compared with the corresponding rate constants for anion formation.     

Untersuchungen an Alkylmetallalkoxiden der Elemente Aluminium,Gallium und Indium. III. Eigenschaften und Schwingungsspektren von Dialkylgallium- und Indiumalkoxiden

Studies on Alkyl Metal Alkoxides of Aluminium, Gallium, and Indium. III. Properties and Vibrational Spectra of Dialkylgallium- and Indium Alkoxides The preparation and the properties of dialkyl metal alkoxides R₂MOR′ (with R = CH₃, CD₃, C₂H₅; R′ = CH₃, CD₃ and M = Ga, In) are described. The vibrational data (IR and Raman) of the trimeric methyl derivatives point to puckered six-membered M₃O₃-ring systems.