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61.
Supercritical fluid extraction (SFE) has been demonstrated to be a useful tool in the determination of additives in polymeric materials. This paper describes the determination of some citrates and benzoates in poly(vinyl chloride) blended with 33–34% of plasticizer using off-line SFE followed by gas chromatography. Experimental factors affecting SFE have been studied by gravimetric analysis, followed by analysis of the extracts using a gas chromatograph equipped with a flame ionization detector. The extraction process is governed by the solubility of the plasticizers in the supercritical fluid or by their diffusion through the polymer matrix, which depend on the pressure and temperature used. Maximum extraction (>99%) is obtained at pressures and temperatures higher than 40 MPa and 80 °C, respectively. Due to purge losses, the collection efficiency of plasticizers into a liquid solvent ranges from 85 to 90%. The applicability of the SFE method is demonstrated using real samples and comparing the results with those obtained by conventional Soxhlet extraction. 相似文献
62.
The thermodynamic model of inorganic arsenic was validated by comparing the predicted As(III) concentration with the experimentally determined one in several river waters samples of the Basque Country (Spain) collected in two sampling campaigns: spring and autumn 2000. This model takes into account the acid-base equilibria of As(III) and As(V) together with the redox equilibria between the H3AsO3 and H3AsO4 species. A correct prediction of As(III) concentration requires the knowledge of the total concentration of arsenic, pH, redox potential (referred to hydrogen electrode), and ionic strength values of the solution. The estimation of the activity coefficients of the arsenic species was performed by means of the Modified Bromley’s Methodology (MBM).In order to perform the experimental As(III) determination, an analytical method was implemented by using an ion exchange separation of As(III)/As(V) on a continuous FIA-IE-HG-AAS system. The total arsenic concentration was determined together with total concentration of the main alkaline or alkaline-earth metals and anions in the natural waters. Temperature compensated measurements of the pH and redox potentials were made in-situ at the sampling sites.For both seasonal campaigns, the agreement between predicted and experimental As(III) is really high for those samples belonging to non polluted river waters. 相似文献
63.
Alberto Avenoza Jesús H Busto Carlos Cativiela Francisco Corzana Jesús M Peregrina María M Zurbano 《The Journal of organic chemistry》2002,67(2):598-601
A short and efficient asymmetric synthesis of the (6R,7S)-7-tert-butoxycarbonylamino-2-ketocarbacepham is described. The key step involves the hetero Diels-Alder reaction of the benzylimine derived from the enantiomer of Garner's aldehyde with Danishefsky's diene. 相似文献
64.
Summary Kinetics of dehydration of equilibrium swollen poly(acrylic acid) hydrogel was investigated using methods of non-isothermal
thermal analysis. Methods of Kissinger, Coats-Redfern, Van Krevelen and Horowitz-Metzger were applied for determination the
kinetics parameters: activation energy (E), pre-exponent (lnA) as well as the kinetics model ƒ(69) for the process of hydrogel dehydration under different heating rates. An existence
of good agreement between determined values of kinetic parameters (Eand A), which were obtained applying different methods under the same heating rate. Functional relationship between changes of
kinetic parameters of dehydration and changes of heating rate was established. An existence of compensation effect is accepted
and explanation of compensation effect appearance during the hydrogel dehydration is suggested. 相似文献
65.
Experiments have been carried out to study the behaviour of organoarsenicals treated with zeolites by means of speciation
analysis. IC-ICP-MS was applied to identify and quantify arsenite, arsenate and the following organoarsenicals: monomethylarsonic
acid (MMA), dimethylarsinic acid (DMA), trimethylarsine oxide (TMAO), tetramethylarsonium bromide (TMA+), arsenobetaine (AsB) and arsenocholine (AsC). Zeolites loaded with ferrous ions did not significantly increase the retention
of inorganic arsenic species compared to the native zeolites, while there was a ten-fold removal of arsenate relating to arsenite.
The formation of As(V) and DMA in the leachates containing clinoptilolites and mordenites was confirmed in the presence of
natural and synthetic zeolites. Arsenobetaine and arsenocholine yielded higher levels of arsenate than the methylated species. 相似文献
66.
D. Reichardt V. Bonačić-Koutecký P. Fantucci J. Jellinek 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1997,40(1):486-489
An ab-initio molecular dynamics procedure without precalculation of the Born-Oppenheimer energy surface based on an iterative non-local density functional method employing Gaussian atomic basis has been developed. Analytical gradients are calculated and used for the propagation of nuclei. Sufficiently long trajectories can be calculated at an acceptable computational cost, allowing for analysis of dynamical behaviour of small metallic clusters. This is illustrated on an example of the Li8 cluster. Temperature behaviour of different type of isomers has been investigated. Calculated power spectra allow to identify the presence of more than one isomeric forms along the given trajectories. 相似文献
67.
María Beatriz de la Calle Guntiñas Michiel Ceulemans Claudia Witte Ryszard Łobiński Freddy C. Adams 《Mikrochimica acta》1995,120(1-4):73-82
A method is presented for the selective determination of the volatile selenium species dimethylselenide and dimethyldiselenide, using a commercially available purge-and-trap injection system coupled to capillary gas chromatography-microwave induced plasma-atomic emission spectrometry. The efficiency of the purging step was evaluated and the parameters affecting the purge and trap processes were optimized. The method was applied to the determination of volatile selenium compounds in lake water. Relative detection limits of 2ng/l for dimethylselenide and dimethyldiselenide, corresponding to an absolute detection limit of 10 pg, were achieved. 相似文献
68.
R.R. Adžić D.N. Simić A.R. Despić D.M. Dražić 《Journal of Electroanalytical Chemistry》1975,65(2):587-601
It was demonstrated that some foreign metal monolayers formed by underpotential deposition have pronounced catalytic effects on the oxidation of formic acid on platinum. The explanation of these effects was sought within the framewor of existing data on the formic acid oxidation and the underpotential deposition. It was found that the catalytic effect of foreign metal monolayers originates in the decrease of hydrogen adsorption thus preventing the formation of the main poisoning species COH. At the same time these experiments confirm the previously postulated mechanism of formation of the poisoning species involving adsorbed hydrogen. 相似文献
69.
del Mar Graciani M Rodríguez A Muñoz M Moyá ML 《Langmuir : the ACS journal of surfaces and colloids》2005,21(16):7161-7169
Micellization in water-ethylene glycol (EG) N-dodecyl, N-tetradecyl, and N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (SB3-12, SB3-14, and SB3-16, respectively) micellar solutions, with the weight percent of EG changing within the range 0-40, was studied by means of surface tension measurements. Information about the influence of the added EG on the aggregation number of the sulfobetaine micelles and on the polarity of the interfacial region of micelles was obtained through fluorescence and spectroscopic measurements. Surface tension measurements also provide information about the dependence of the surface excess concentration, the minimum area per surfactant molecule, the surface pressure at the cmc, and the standard Gibbs energy of adsorption on the added weight percent of the organic solvent. The Gordon parameter of the water-EG mixtures was also estimated by means of surface tension measurements. The thermodynamic and structural changes originated by the presence of EG control the micellar kinetic effects observed in the reaction methyl 4-nitrobenzenesulfonate + Br(-) occurring in the water-EG sulfobetaine micellar solutions. Information about the distribution of bromide ions between the bulk and micellar pseudophases was obtained through conductivity measurements. The kinetic micellar effects were quantitatively explained by using the pseudophase kinetic model. 相似文献
70.
Aleksandar Ivić 《Monatshefte für Mathematik》1987,104(1):17-27
The existence of zeros ofZ
(k)(t) in short intervals of the type [T, T+H] is established, whereHT
a(k)logT,
. Hitherto the sharpest bounds for the constanta(k) are obtained by employing a certain exponential averaging technique and the estimation of the relevant exponential sums. Bounds for
are also derived, under the assumption that
orZ(t) does not vanish in certain short intervals. 相似文献