Determination of diethanolamine or <Emphasis Type="Italic">N</Emphasis>-methyldiethanolamine in high ammonium concentration matrices by capillary electrophoresis with indirect UV detection: application to the analysis of refinery process waters

Alkanolamines such as diethanolamine (DEA) and N-methyldiethanolamine (MDEA) are used in desulfurization processes in crude oil refineries. These compounds may be found in process waters following an accidental contamination. The analysis of alkanolamines in refinery process waters is very difficult due to the high ammonium concentration of the samples. This paper describes a method for the determination of DEA in high ammonium concentration refinery process waters by using capillary electrophoresis (CE) with indirect UV detection. The same method can be used for the determination of MDEA. Best results were achieved with a background electrolyte (BGE) comprising 10 mM histidine adjusted to pH 5.0 with acetic acid. The development of this electrolyte and the analytical performances are discussed. The quantification was performed by using internal standardization, by which triethanolamine (TEA) was used as internal standard. A matrix effect due to the high ammonium content has been highlighted and standard addition was therefore used. The developed method was characterized in terms of repeatability of migration times and corrected peak areas, linearity, and accuracy. Limits of detection (LODs) and quantification (LOQs) obtained were 0.2 and 0.7 ppm, respectively. The CE method was applied to the determination of DEA or MDEA in refinery process waters spiked with known amounts of analytes and it gave excellent results, since uncertainties obtained were 8 and 5%, respectively.     

Preliminary characterization of anhydrous ethanol used in Brazil as automotive fuel

This work reports preliminary studies on the characterisation of anhydrous ethanol (AEA) used as an automotive fuel mixed with gasoline in Porto Alegre (South Brazil). Pre-concentration of the impurities contained in 1000 ml of AEA was carried on through solid-phase extraction using XAD4 resin. The main compounds in the extract were identified by means of spectral data from the library of the equipment. The concentrate was then fractionated using a preparative liquid chromatographic column filled with activated silica gel and the elution procedure was carried out with, n-hexane, n-hexane-benzene (1:1, v/v) and dichloromethane. Prior to analysis by GC-MS, each fraction was reduced to 1 ml with a gentle stream of nitrogen. Saturated linear hydrocarbons and aromatic hydrocarbons eluted in the first fraction and oxygenated compounds such as aldehydes. ketones and alcohols, eluted in the second one. were the main compounds detected in the sample.     

NMR-Spektren vontrans—Chalcon-oxim,-semicarbazon und-thiosemicarbazon und ihren cyclischen Isomeren (3,5-Diphenyl-2-isoxazolin und 1-substituierte 3,5-Diphenyl-2-pyrazoline)

Zusammenfassung Frühere Strukturvorschläge für dastrans-Chalcon-oxim, semicarbazon und thiosemicarbazon¹ werden mit Hilfe von NMR-Spektren richtiggestellt: Die sauer katalysierte Reaktion führt zwar zum Oxim, Semicarbazon und Thiosemicarbazon destrans-Chalcons; basische Katalysatoren bewirken dagegen eine interne Cyclisierung zu 3,5-Diphenyl-2-isoxazolin bzw. zu 1-substituierten 3,5-Diphenyl-2-pyrazolinen. Die Zuordnungen in den NMR-Spektren wurden durch Vergleich mittrans-Dypnon und seinem Semicarbazon getroffen.

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NMR spectra of trans-chalcone oxime, semicarbazone and thiosemicarbazone and their cyclic isomers (3,5-diphenyl-2-isoxazoline and 1-substituted 3,5-diphenyl-2-pyrazolines)

Earlier tentatively assigned structures fortrans-chalcone oxime, semicarbazone and thiosemicarbazone, resp., have been corrected by means of NMR spectra: open-chain structures have been found for the title compounds formed in the acid catalyzed reaction, whereas basic catalysts lead to intramolecular cyclization with formation of 3,5-diphenyl-2-isoxazoline and 1-substituted 3,5-diphenyl-2-pyrazolines resp. Assignments in the NMR spectra were made by comparison with those from authentic samples oftrans-dypnone and its semicarbazone.

     

Functionalization of single-walled carbon nanotubes via the Bingel reaction

Single-walled carbon nanotubes have been cyclopropanated under Bingel reaction conditions, and the functionalized nanotubes have been characterized by atomic force microscopy using "chemical tagging" techniques.     

Existence of rank 3 vector bundles with given chern classes on homogeneous rational 3-folds

One proves that any rank 3 topological vector bundle on a homogeneous rational 3-fold has an algebraic structure. The proof uses extensions of ideals by rank 2 vector bundles. The paper also contains a construction of rank 3 vector bundles on 3-folds using extensions of ideals by rank 2 reflexive sheaves.     

One-Step Synthesis of Monolithic Silica Nanocomposites in Fused Silica Capillaries

The ideal way to prepare efficient, yet robust stationary phases for microanalytical high-resolution methods such as capillary chromatography and electrochromatography remains to be defined. In this contribution a one step sol-gel process is proposed for the production of monolithic, macroporous nanocomposite phases in fused silica capillaries, which require no additional derivatization, since they already bear the interactive (C8) moieties. The effect of the catalyst, the water content, the pH, as well as that of certain additives on monolith formation and porosity is investigated. Volume shrinkage and a tendency to crack were the major obstacles to overcome. Homogeneous stationary phases could be produced by applying a pH gradient during sol formation, thereby changing the catalytic principle from acidic (0.1 M HCl) to basic (gradual formation of OH^– as a consequence of the hydrolysis of N-methylformamide). Gelation/coacervation of suchgels could be induced by the addition of N,N-diethylamine. The water content during sol formation was determined as decisive for pore formation, with 250% of the amount theoretically needed for complete hydrolysis of all precursors giving optimal results. The volume shrinkage problem during xerogel formation was resolved by integrating dialkyldialkoxysilane units (dimethyldiethoxysilane 35 mol%) into the silica network.     

Behaviour of Pluronic P84 block copolymer micelles above the gelification temperature as probed by positron annihilation lifetime spectroscopy

The new method based on positron annihilation lifetime spectroscopy (PALS) to determine both the mean core radius, R(core), and aggregation number, N(ag), of micelles is applied to the study of aqueous solutions of the triblock Pluronic P84 copolymer as a function of temperature (T), beyond the gelification point (334 K). Two long-lived components appear in the PALS spectra, ascribed to triplet positronium in the water bulk (o-Ps(aq)) and in the organic core of the micelles (o-Ps(org)). Of the various fitting parameters, only the lifetime of the latter species, tau4, and the micellar parameters, R(core) and N(ag), disclose the occurrence of gelification by first increasing up to 334 K, then decreasing. By contrast to what is known in case of phase transition, none of the parameters shows any abrupt change at 334 K, whereas the macroscopic viscosity of the solutions suffers a drastic increase. This is attributed to the fact that positronium is sensitive to the microviscosity of the solutions. At the transition point, the properties of the polyoxipropylene aggregates forming the organic core of the P84 micelles are not greatly affected. Furthermore, the fact that the experimental N(ag) values coincide with those calculated for spheres, from the R(core) values, indicates that the shape of the P84 cores does not change significantly after gelification. The onset of gelification results from a decrease in the hydrogen bonding interactions in the solution with an ensuing relative increase in the interactions between the polyoxipropylene (PPO) groups, initially forming the corona of the P84 micelles, in an intermicellar mode. This increased solicitation of the PPO groups outside their initial location would result in depletion in the number of surfactant molecules forming the micelles, viz. a decrease in both R(core) and N(ag) above 334 K. From the data, additional information can be gained regarding the local viscosity and surface tension in the micellar cores.