A density functional theory study of the a-olefin selectivity in Fischer-Tropsch synthesis

We studied the alpha-olefin selectivity in Fischer-Tropsch (FT) synthesis using density functional theory (131717) calculations. We calculated the relevant elementary steps from C-2 to C-6 species. Our results showed that the barriers of hydrogenation and dehydrogenation reactions were constant with different chain lengths, and the chemisorption energies of alpha-olefins from DFT calculations also were very similar, except for C-2 species. A simple expression of the paraffin/olefin ratio was obtained based on a kinetic model. Combining the expression of the paraffin/olefin ratio and our calculation results, experimental findings are satisfactorily explained. We found that the physical origin of the chain length dependence of paraffin/olefin ratio is the chain length dependence of both the van der Waals interaction between adsorbed alpha-olefins and metal surfaces and the entropy difference between adsorbed and gaseous alpha-olefins, and that the greater chemisorption energy of ethylene is the main reason for the abnormal ethane/ethylene ratio. (c) 2008 Elsevier Inc. All rights reserved.

A modified commercial DRIFTS cell for kinetically relevant operando studies of heterogeneous catalytic reactions

This paper discusses a number of checks that should be carried out to ensure that the kinetic and spectroscopic measurements made using a DRIFTS cell are meaningful. The observations reported here demonstrate how an appropriately modified commercial DRIFTS cell can provide pertinent kinetic information about both gaseous products and the related surface intermediates. The oxidation of CO with 02 was used as a test to assess the catalyst bed bypass by the reaction mixture. Full CO conversion was obtained after the light-off temperature in the case of the modified cell, contrary to the case of the original cell, for which 80% of the reaction mixture bypassed the catalyst bed. The water-gas shift reaction over a Pt/CeO2 catalyst was used as a model reaction to further characterize the behavior of the cell under reaction conditions. The catalyst bed was shown not to be a dead-zone and was purged in essentially the same time as that needed to purge the cell. The reaction chamber globally operated in a quasi plug-flow mode and the gas composition in the thin catalyst bed appears to be homogeneous when operated under differential conditions. The production of the gas-phase reaction product CO2 could be simultaneously followed both by mass spectrometry and DRIFTS, both techniques leading to identical results. Various IR bands integration methods were discussed to allow a precise and accurate determination of the surface concentration of adsorbates during isotopic exchange. (c) 2008 Elsevier B.V. All rights reserved.

The impact and recovery of asteroid 2008 TC3

In the absence of a firm link between individual meteorites and their asteroidal parent bodies, asteroids are typically characterized only by their light reflection properties, and grouped accordingly into classes. On 6 October 2008, a small asteroid was discovered with a flat reflectance spectrum in the 554-995nm wavelength range, and designated 2008 TC3 (refs 4-6). It subsequently hit the Earth. Because it exploded at 37km altitude, no macroscopic fragments were expected to survive. Here we report that a dedicated search along the approach trajectory recovered 47 meteorites, fragments of a single body named Almahata Sitta, with a total mass of 3.95kg. Analysis of one of these meteorites shows it to be an achondrite, a polymict ureilite, anomalous in its class: ultra-fine-grained and porous, with large carbonaceous grains. The combined asteroid and meteorite reflectance spectra identify the asteroid as F class, now firmly linked to dark carbon-rich anomalous ureilites, a material so fragile it was not previously represented in meteorite collections.

Review of Periodical Literature Published in 2008 (VI Since 1945)

NA

The feminine character and temporal freedom in three historical novels by Angelina Muñiz: Morada interior (1972), "El Mercader de Tudela" (1995) y "La Burladora de Toledo" (2008)

We focus on the representation of time in Muñiz’s historical novels. Concretely, we stress the attitude of the feminine characters towards time and history. Muñiz’s female personages continuously transgress temporal borders and move freely between different historical periods. We relate Muñiz’s particular vision on time and on the separation lines between historical periods to her situation as an exile. The author is continuously crossing borders between the past of her homeland and the present of her adoptive country. We argument Muñiz is recreating this “borderfree” attitude towards time in the female characters of her historical novels.