Pseudo-steady-state solutions for solidification in a wedge

Polubarinova-Kochina's analytical differential equation methodis used to determine the pseudo-steady-state solution to problemsinvolving the freezing (solidification) of wedges of liquidwhich are initially at their fusion temperature. In particular,we consider four distinct problems for wedges which are: freezingwith the same constant boundary temperature, freezing with thesame constant boundary heat fluxes, freezing with distinct constantboundary temperatures and freezing with distinct constant fluxesat the boundaries. For the last two problems, a Heun's differentialequation with an unknown singularity is derived, which in bothcases admits a particularly elegant simple solution for thespecial case when the wedge angle is . The moving boundariesobtained are shown pictorially.     

Formation of XeCl− in the gas phase

Ion cyclotron resonance has been used to detect the formation of XeCl^? at pressure 10^?4 torr from the ion-molecule reaction of COCl^? and Xe. The dissociation energy of XeCl^? into Xe and Cl^? is estimated to be less than 10 kcal/mole. The results suggest that other negative ions similar to XeCl^? may be detected by mass spectrometric techniques.     

Ab initio analysis of some fluoride and oxide structures doped with Pr and Yb

Doping effects are analyzed by means of the ab initio perturbed ion (aiPI) method via substitution of the fluorides and oxides of zirconium, hafnium, and thorium. Lattice relaxation is simulated through the calculation of vibrational breathing modes and substitutional effects on the compound are thereby analyzed. In addition, the band gaps (in the pure species) and impurity levels (where substitutional ions Pr⁺⁴ and Yb⁺³ are considered in the doped species) of the fluorides are estimated via the transition energy calculated at the aiPI‐optimized geometry of the pure and doped crystal clusters by means of the configuration interaction with single excitations (CIS) method that accounts for electronic correlation. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2004     

Methodology for processing backscattered electron images. Application to Aguada archaeological paints

Scanning electron microscopy is a powerful technique in several fields of science and technology. In particular it is an important complement in the characterization of materials for which X-ray analysis is not possible. Such is the case of thin paint layers on ceramic pots, in which, even for low incident energies, the electron interaction volume can be greater than the paint thickness—in addition to the problem arising from similar compositions. With the aim of complementing other common techniques used in compositional materials characterization, in this work, an image-processing software has been developed, which implements a new methodology for the treatment of backscattered electron (BSE) images in order to bring to evidence small mean atomic number contrasts, usually imperceptible to human eye. The program was used to study black and white pigments of ceramic pieces belonging to the Ambato style of “Aguada” culture (Catamarca province, Argentina, IV–XII centuries AD). Although the BSE images acquired for these samples showed no apparent contrast between sherd and black and white pigments, through image-processing algorithms using different space filters, chemical contrast between regions has been brought to evidence with a minor detail loss. This has been accomplished by applying a smoothing filter, after which the main routine for contrast enhancement reveals details in the grey-level region of interest; finally, a filter for edge enhancement permits to recover some details lost in the previous steps, achieving satisfactory results for the painted sherd samples analyzed. In order to validate the mean atomic number differences found between each pigment and the ceramic body, X-ray diffraction diagrams have been refined with Rietveld method using the software DIFFRACplus Topas^®, arriving to mineralogical differences which agree with the results obtained. As a consequence of this study, the program developed has proven to be a suitable tool for routine analysis of samples with slight chemical contrast.     

Dynamic Effects Dictate the Mechanism and Selectivity of Dehydration–Rearrangement Reactions of Protonated Alcohols [Me2(R)CCH(OH2)Me]+ (R=Me,Et, iPr) in the Gas Phase

The gas‐phase dehydration–rearrangement (DR) reactions of protonated alcohols [Me₂(R)CCH(OH₂)Me]⁺ [R=Me ( ME ), Et ( ET ), and iPr ( I‐PR )] were studied by using static approaches (intrinsic reaction coordinate (IRC), Rice–Ramsperger–Kassel–Marcus theory) and dynamics (quasiclassical trajectory) simulations at the B3LYP/6‐31G(d) level of theory. The concerted mechanism involves simultaneous water dissociation and alkyl migration, whereas in the stepwise reaction pathway the dehydration step leads to a secondary carbocation intermediate followed by alkyl migration. Internal rotation (IR) can change the relative position of the migrating alkyl group and the leaving group (water), so distinct products may be obtained: [Me(R)CCH(Me)Me ??? OH₂]⁺ and [Me(Me)CCH(R)Me ??? OH₂]⁺. The static approach predicts that these reactions are concerted, with the selectivity towards these different products determined by the proportion of the conformers of the initial protonated alcohols. These selectivities are explained by the DR processes being much faster than IR. These results are in direct contradiction with the dynamics simulations, which indicate a predominantly stepwise mechanism and selectivities that depend on the alkyl groups and dynamics effects. Indeed, despite the lifetimes of the secondary carbocations being short (<0.5 ps), IR can take place and thus provide a rich selectivity. These different selectivities, particularly for ET and I‐PR , are amenable to experimental observation and provide evidence for the minor role played by potential‐energy surface and the relevance of the dynamics effects (non‐IRC pathways, IR) in determining the reaction mechanisms and product distribution (selectivity).     

Gas-phase electrophilic addition promoted by CH(3)S(+)=CH(2) ions on aromatic systems

The gas-phase methylenation reaction between CH(3)S(+)=CH(2) and alkylbenzenes, aniline, phenol and alkyl phenyl ethers, which yields [M + CH](+) and CH(3)SH, has been studied by Fourier transform ion cyclotron resonance (FT-ICR) techniques and computational chemistry at the DFT level. The methylthiomethyl cation is less reactive than methoxymethyl and, unlike the latter, is unreactive toward benzene. The calculations suggest that reaction with toluene should proceed primarily by addition at the para and ortho positions resulting in a benzyl-type ion. Reaction with aniline-2,3,4,5,6-d(5) reveals that elimination of CH(3)SD is kinetically favored by a factor of 5 over elimination of CH(3)SH. Experiments with C(6)H(6)ND(2) and theoretical calculations suggest that methylenation at the nitrogen atom is energetically favorable and likely, but the observed results may reflect some H/D scrambling, which occurs after attack at a ring position. By comparison, reaction with phenol-2,3,4,5,6-d(5) reveals that methylenation followed by elimination of CH(3)SD is kinetically favored by a factor of 3.8 over elimination of CH(3)SH. For phenol, the theoretical calculations suggest that attack by CH(3)S(+)=CH(2) at the para or ortho position is the only low-energy pathway for methylenation. However, a low-energy pathway for hydrogen scrambling is predicted by the calculations originating from the exit complex, [CH(3)SH(...) CH(2)=C(6)H(4)=OH](+), of reaction at a ring position.     

Comparison between XRF and EPMA applied to study the ionic exchange in zeolites

Zeolites are crystalline aluminosilicates consisting of SiO₄ and AlO₄ tetrahedral as primary units. One peculiar characteristic of zeolites is the ion exchange capacity defined as the capacity to locate specific cations in the framework of zeolites; it depends on the chemical composition and varies with the structure of the zeolite and with the cation nature. This work studies the exchange of the Na⁺ monovalent cation of 5A and 13X synthetic zeolites by the Ca²⁺ bivalent cation present in a CaCl₂ solution. X‐ray fluorescence (XRF) and electron probe microanalysis (EPMA) techniques were used to determine the cation exchange capacity (CEC). The efficiencies of the two X‐ray detectors were compared and the minimum detection limits of the zeolite elements were calculated. Although both techniques differ in the sample excitation mode, the results obtained were compatible. The results showed that the CEC was higher for the 5A zeolite, in agreement with its lower SiO₂/Al₂O₃ ratio and its greater BET area. It was also found that the amount of Na⁺ ions exchanged by Ca²⁺ ions was in complete agreement with the corresponding molar balance. The determination of the CEC using X‐ray spectroscopy techniques can be considered a novelty as XRF and EPMA techniques permit to analyze the sample directly. Copyright © 2009 John Wiley & Sons, Ltd.