Thermal decomposition of sodium nitrite and sodium nitrate pre-adsorbed on TiO2 surfaces

The thermal decomposition of sodium nitrite or nitrate pre-adsorbed upon TiO₂ surfaces has been investigated by employing several techniques as infrared spectroscopy (IR) and temperature programmed desorption in conjunction with mass spectrometry analysis (TPD-MS) to study the features observed during these thermal decompositions. Differential thermal analysis (DTA) in combination with X-ray diffraction analysis (XRD) were used to investigate the possibility of a solid state chemical reaction between the solid products originated from the thermal decomposition of the pre-adsorbed species and the TiO₂. On the basis of our results, various characteristic features of these thermal decomposition reactions will be discussed.This work was supported by JUNTA DE ANDALUCIA (financial support for research groups/1990).     

Synthesis of 6-Ami NO-5-Nitro-4-Thi Oxopyri Mi Dines

The synthesis of 6-ami no-5-nitro-4-thioxo-pyrimidines starting from the C-adducts of nitro-keteneaminals and acyl isothiocyanates is described.     

Determination of trace amounts of cobalt in water by solid-phase spectrophotometry after preconcentration on a nitroso R salt chelating resin

A sensitive method for the determination of microamounts of cobalt by ion-exchanger spectrophotometry has been developed. The chromogenic agent, Nitroso-R-Salt (NRS), was loaded on an anionic-exchange resin (Amberlite CG-400). The absorbance of the NRS-cobalt complex on the chelating resin was measured at 508 nm. The best conditions for the preconcentration of cobalt on the resin before the spectrophotometric determination were a pH value of 6, temperature of 80 °C, and heating times of 45 or 90 min for 50 and 400 ml of sample, respectively. The detection limits were 27 ng/ml (50-ml samples) and 1.8 ng/ml (400-ml samples). Interference by other metals was investigated. The method is useful for determination of cobalt in natural waters.     

Extraction of Strontium and Cesium by Dicarbollides, Crown Ethers and Functionalized Calixarenes

The two main classes of extractantsused for the extraction of cesium and strontium aredicarbollides and crown ethers. Dicarbollides wereused on a large scale for the extraction of these twoelements from high-activity waste. The basicdicarbollides present drawbacks since they need to bediluted in polar solvent such as nitrobenzene and theirefficiency strongly decreases as the acidity of liquidwaste increases. Crown ethers enable cesium andstrontium to be extracted if the concentration ofsodium or the acidity of solutions are not too high.Recently, calixarenes blocked in the 1,3-alternateconformation were used for the selective extractionof cesium, even from high-salt waste matrices.     

On higher order Stickelberger-type theorems

We discuss an explicit refinement of Rubin?s integral version of Stark?s conjecture. We prove that this refinement is a consequence of the relevant case of the Equivariant Tamagawa Number Conjecture of Burns and Flach, hence obtaining a full proof in several important cases. We also derive several explicit consequences of this refinement concerning the annihilation as Galois modules of ideal class groups by explicit elements constructed from the values of higher order derivatives of Dirichlet L-functions. We finally describe the relation between our approach and those found in recent work of Emmons and Popescu and of Buckingham.     

Single‐Site Zeolite‐Anchored Organoiridium Carbonyl Complexes: Characterization of Structure and Reactivity by Spectroscopy and Computational Chemistry

A family of HY zeolite‐supported cationic organoiridium carbonyl complexes was formed by reaction of Ir(CO)₂(acac) (acac=acetylacetonate) to form supported Ir(CO)₂ complexes, which were treated at 298 K and 1 atm with flowing gas‐phase reactants, including C₂H₄, H₂, ¹²CO, ¹³CO, and D₂O. Mass spectrometry was used to identify effluent gases, and infrared and X‐ray absorption spectroscopies were used to characterize the supported species, with the results bolstered by DFT calculations. Because the support is crystalline and presents a nearly uniform array of bonding sites for the iridium species, these were characterized by a high degree of uniformity, which allowed a precise determination of the species involved in the replacement, for example, of one CO ligand of each Ir(CO)₂ complex with ethylene. The supported species include the following: Ir(CO)₂, Ir(CO)(C₂H₄)₂, Ir(CO)(C₂H₄), Ir(CO)(C₂H₅), and (tentatively) Ir(CO)(H). The data determine a reaction network involving all of these species.