Numerical simulation of free-surface thermally influenced flows for nonhomogeneous fluids

A finite-difference technique is presented to simulate the behavior of natural water bodies under the influence of pollutants and temperature differences. The mathematical model, which has been discretized, is the closed system obtained by combining the Navier-Stokes equations, the heat transfer equation, the diffusion equations, and an equation relating the fluid density to both the chemical concentration and the temperature. The numerical method is based on the marker-and-cell method, which has been extended to consider the volume expansion due to heat transfer and the density variations.     

The state of 57Fe in pure and oxidized tin chalcogenides by Mössbauer spectroscopy

A Mössbauer spectroscopy study has been made of the stabilization states of ⁵⁷Fe in pure tin chalcogenides. The values of the isomer shifts and the quadrupole splittings lead to the conclusion that iron presents the electronic configuration 3d⁵4s^x at high spin in the interstitial position. This result is confirmed varying the ⁵⁷Fe neighbours by partial substitution of tellurium with oxygen. In this case, too, the values of Mössbauer parameters confirm the same results. The quadrupole moment present in pure SnTe doped ⁵⁷Co, and the shift of isomer shift towards less positive values for the oxidizated samples have been qualitatively justified as well.     

Carbon-13 NMR characterisation of carboxyl derivatives of 1-ureidopyrroles

1-Ureido-5-methyl-2,3-dicarbethoxypyrrole under acidic conditions afforded different partially hydrolyzed or decarboxylated products. It has been possible to characterize two isomeric monoethyl esters of dicarboxylic acids of 1-ureidopyrroles by proton gated decoupled carbon-13 nmr spectra on the basis of multiplicities of the carbonyl carbons resonances.     

Oxidation of tertiary polycycl1c amines by RuO4

The reactions of certain tertiary polycyclic amines such as N-benzyl-9-azabicy-clo- [3,3,1]-nonane, N-benzyl-5, 6-dihydro-11H-dibenz [b,e] azepine, and N-benzyl-1,2,3,4-tetrahydroisoquinoline with ruthenium tetroxide, taking place in both heterogeneous and homogeneous systems, have made it possible to establish the order of reactivity of the various methylene groups adjacent to the nitrogen with respect to this oxidizing agent.     

Diffusion-controlled solid-state reactions of spherical particles, a general model for multiphase binary systems

The formal treatment of the diffusion-controlled growth of n binary compounds with narrow homogeneity range during the reaction of a sphere of reactant A immersed in reactant B is presented and discussed. Both constituents are assumed to be mobile. The reaction products are assumed to grow simultaneously as uniform and compact concentric layers with ideal contact at the interfaces as well as at the external surface of the sphere. The kinetic equations follow from the coupling between chemical reactions and partitioning of the diffusion flux at phase boundaries. The results for the formation of two and three compounds are presented. The influence of the initial radius of the sphere, of the relative magnitude of the kinetic constants, and of the volume variation is discussed in detail.     

Dielectric properties of high-kappa oxides: theory and experiment for Lu2O3

We present a combined experimental and theoretical analysis of the dielectric and vibrational properties of crystalline lutetium oxide in its ground-state bixbyite structure. The vibrational dielectric function of Lu2O3 thin films grown by atomic-layer deposition was studied by infrared transmission and reflection-absorption spectroscopies, selectively accessing transverse and longitudinal optical frequencies. The static dielectric constant is extracted analyzing the infrared response. We also present first-principles density-functional linear-response calculations, which are in close agreement with experiment, and provide insight into the microscopic nature of vibrational spectra and dielectric properties.     

Thiazolidin-4-one formation. Mechanistic and synthetic aspects of the reaction of imines and mercaptoacetic acid under microwave and conventional heating

Microwave irradiation of a mixture of benzylidene-anilines and mercaptoacetic acid in benzene gives 1,3-thiazolidin-4-ones in very high yield (65-90%), whereas the same reaction performed through using the conventional method, at reflux temperature, requires a much longer time and gives a much lower yield (25-69%). This difference seems to be due to some intermediates and by-products formed during the conventional reaction. On the basis of 1H NMR studies, two different mechanisms, acting in benzene and in DMF, respectively, have been hypothesized for the thiazolidin-4-one system formation.     

Monolithic columns with a gradient of functionalities prepared via photoinitiated grafting for separations using capillary electrochromatography

Stationary phases for capillary electrochromatography with a longitudinal gradient of functionalities have been prepared via photoinitiated grafting of polymer chains onto the pore surface of a porous polymer monolith. In order to achieve the desired retention and electroosmotic flow, the hydrophobic poly(butyl methacrylate-co-ethylene dimethacrylate) monolith with optimized porous properties was grafted with a layer of ionizable polymer, poly(2-acrylamido-2-methyl-1-propanesulfonic acid). A moving shutter and a neutral density filter were used to control the dose of UV light received at different locations along the monolith in order to create the longitudinal gradient of functionalities. Formation of the desired gradients was confirmed using electron probe microanalysis of different locations along the column. The preparation technique significantly affects performance in the CEC mode as demonstrated on the separations of a model mixture using columns both with homogeneous distribution of grafts and with a gradient of functionality. Columns grafted with the gradient of functionalities were found superior to those functionalized uniformly. A comparison of the performance of the gradient column with another containing evenly distributed functionalities showed the performance benefits of the "gradient" column.