Nucleation of isolated PO4 units on CeO2 driven by high temperatures and the effect on its oxygen storage and release properties

The chemical nature of P-containing species of varying concentration present in CeO₂ after impregnation with (NH₄)₂HPO₄ and calcination at 1273 K, and their effects on the oxygen storage and release (OSR) properties of ceria are reported for the first time. The samples were characterized by different techniques and the results were compared with those recently reported on the same samples but calcined at 873 K. When P-containing ceria solids were calcined at 1273 K, CePO₄ (monazite) was the predominant P-containing species on the surface of ceria, confirming previous studies that showed that monazite exists for those samples in which the surface P loading (P atoms per nm⁻²) is larger than 5.5. For lower surface P concentrations, isolated orthophosphate units are present at the surface and within the subsurface region of the solid. Severe sintering of CeO₂ after calcination at 1273 K resulted in P concentrations >5.5 P atoms·nm⁻² in all samples. Isolated PO₄ units that could initially be present in the samples calcined at 873 K nucleated and CePO₄ was formed when samples were calcined at 1273 K. OSR properties of CeO₂ deteriorated progressively when P loading increased due to the presence of larger crystals of the very stable Ce(III) phase of CePO₄ at the surface of the P-containing ceria solids.     

Parameter Identification in Photothermal Imaging

We propose a technique to reconstruct the geometry of inclusions and their material parameters in thermal scattering near surfaces. The imaging problem is reformulated as a constrained optimization problem with a finite number of stationary constraints. The unknown domains and their parameters are the design variables. A descent method combining topological derivative analysis to find improved guesses of the objects and gradient iterations to correct their material parameters provides reasonable reconstructions.     

NMR chemical shift reagents in structural determination of lipid derivatives: IV. Methylcis- andtrans-9,10-epoxystearate and methylerythro- andthreo-9,10-dihydroxystearate

Chemical shift reagents were used to expand the amount of structural information obtainable from NMR studies of derivatives of methyl oleate and elaidate:methylcis-9,10-epoxystearate, methyltrans-9,10-epoxystearate, methyl erythro-9,10-dihydroxystearate, and methyl threo-9,10-dihydroxystearate. Chemical shift reagent studies of methyltrans-9,10-epoxystearate and methyl threo-9,10-dihydroxystearate afforded the most information. Chemical shift reagent studies of methylcis-9,10-epoxystearate and methyl erythro-9,10-dihydroxystearate were decidedly inferior. The series of complementary interpretive techniques previously developed during chemical shift reagent studies of monofunctional fatty esters and model polyfunctional fatty esters were found to be applicable in the current study. However, to avoid ambiguity in several proton assignments, supplementary spin decoupling experiments were necessary.     

Esters of hydroxystearic acids as primary low-temperature plasticizers for a vinyl chloride—Vinyl acetate copolymer

Summary Thirty-one acyloxy or aryloxy esters prepared from hydroxystearic acids have been evaluated as plasticizers for a vinyl chloride-vinyl acetate copolymer (95∶5). Many of them were found to be primary plasticizers, having outstanding low-temperature performance when employed at the 35% level. Formulations with these compounds compared quite favorably in tensile properties with those containing the di-2-ethylhexyl esters of phthalic, sebacic, azelaic, and adipic acids. Volatility losses were similar to those of the four di-2-ethylhexyl esters. The loss of plasticizer through migration was equal to or less than that from compositions containing the esters of sebacic, azelaic, and adipic acids but was greater than that of the phthalate ester. A mechanistic scheme of plasticizer-polymer interaction has been presented, proposing that the rate of diffusion of plasticizer through the polymer mass is a controlling factor in both good low-temperature performance and the resulting high migration losses. Methyl esters, some aromatic esters, and esters containing three or more polar centers have improved permanence but show a more rapid change in torsional modulus as the temperature is lowered during the determination of the Clash-Berg stiffening temperature. Eastern Utilization Research and Development Division, Agricultural Research Service, U. S. Department of Agriculture.     

Coking kinetics of a Cr2O3/Al2O3 catalyst during 1-butene dehydrogenation: Effect of H2 partial pressure

The influence has been studied of the partial pressure of hydrogen (0–30 kPa) upon the coking rate of a Cr₂O₃/Al₂O₃ commercial catalyst during 1-butene dehydrogenation. Coke deposition has been analysed using a monolayer-multilayer reversible coke growth model (MMRC model). This model provides good fits to the experimental data, within the range of partial pressure of H₂ studied, and allows us to estimate the main kinetic parameters involved in the coking-deactivation process. The results obtained reveal a dual effect of hydrogen: competition against 1-butene for the active sites and the removal of coke precursors from the catalyst surface. Bom effects diminish the coking rate as the H₂ partial pressure is increased.     

Impregnation of X Zeolite with Alkaline Hydroxide During the Synthesis

Enhancement of the basic properties of the X zeolite with FAU framework has been carried out during synthesis, without further treatment such as ion-exchange or impregnation. Control of the washing stage enables retention of the optimum amount of alkaline hydroxides, which increases the basic catalytic activity of X zeolite in the alkylation of toluene. This alkaline hydroxides neither affect the FAU framework nor the silicon/aluminium molar ratio of the X zeolite. The optimum (Na + K)/Al molar ratio of the improved catalyst was 1.06 corresponding to a washing volume of 200 mL. This X zeolite presented better catalytic activity than a cesium-zeolite prepared by ion-exchange. The presence of hydroxysodalite impurity in the X zeolite increased the amount of impregnated alkaline hydroxides but not the catalytic activity. The present study shows that it is possible to increase the basic properties of the X zeolite directly in the synthesis process.     

A SIMPLE METHOD FOR STUDYING THE KINETICS OF GAS-SOLID REACTIONS IN A FLUIDIZED BED REACTOR

A methodology for studying the kinetics of gas-solid reactions in a fluidized bed reactor is presented. This procedure is based on the analysis of the response of the system (flue gases) when batches of solids of different weight are added to the reactor. The method has been applied to the study of limestone particle calcination. The calcination rate constants obtained are in good agreement with those found in the literature. The method offers the advantage of simplicity and avoids the use of model assumptions or empirical correlations.     

A three-parameter equation for molecular weight distribution of low-density polyethylene

A new three-parameter distribution function is proposed which fits best the experimental molecular weight distribution curves of branched lowdensity polyethylenes. The data were interpreted from GPC measurements, and a special computer program was utilized in order to derive the best values of the empirical constants a, b, and c.     

Kinetics of the decomposition of total aliphatic waxes in olive oil during deodorization

Changes in the content of aliphatic waxes during industrial deodorization and/or physical refining of bleached olive oil were studied in an experimental discontinuous pilot plant of 250 kg deodorizer using nitrogen as stripping gas in place of steam. The kinetic constants for the decomposition of waxes during the deodorization process were determined. The reaction orders studied are zero (or can be considered zero) within the working interval. The values of rate constants, activation energy, frequency factor, increment of activation Gibbs free energy, activation enthalpy, and activation entropy are established.