Inelastic neutron scattering studies of methyl chloride synthesis over alumina

Not only is alumina the most widely used catalyst support material in the world, it is also an important catalyst in its own right. One major chemical process that uses alumina in this respect is the industrial production of methyl chloride. This is a large scale process (650 000 metric tons in 2010 in the United States), and a key feedstock in the production of silicones that are widely used as household sealants. In this Account, we show how, in partnership with conventional spectroscopic and reaction testing methods, inelastic neutron scattering (INS) spectroscopy can provide additional insight into the active sites present on the catalyst, as well as the intermediates present on the catalyst surface.<p></p> INS spectroscopy is a form of vibrational spectroscopy, where the spectral features are dominated by modes involving hydrogen. Because of this, most materials including alumina are largely transparent to neutrons. Advantageously, in this technique, the entire “mid-infrared”, 0–4000 cm<sup>–1</sup>, range is accessible; there is no cut-off at 1400 cm<sup>–1</sup> as in infrared spectroscopy. It is also straightforward to distinguish fundamental modes from overtones and combinations. <p></p> A key parameter in the catalyst’s activity is the surface acidity. In infrared spectroscopy of adsorbed pyridine, the shifts in the ring stretching modes are dependent on the strength of the acid site. However, there is a very limited spectral range available. We discuss how we can observe the low energy ring deformation modes of adsorbed pyridine by INS spectroscopy. These modes can undergo shifts that are as large as those seen with infrared inspectroscopy, potentially enabling finer discrimination between acid sites. <p></p> Surface hydroxyls play a key role in alumina catalysis, but in infrared spectroscopy, the presence of electrical anharmonicity complicates the interpretation of the O–H stretch region. In addition, the deformations lie below the infrared cut-off. Both of these limitations are irrelevant to INS spectroscopy, and all the modes are readily observable. When we add HCl to the catalyst surface, the acid causes changes in the spectra. We can then deduce both that the surface chlorination leads to enhanced Lewis acidity and that the hydroxyl group must be threefold coordinated. <p></p> When we react η-alumina with methanol, the catalyst forms a chemisorbed methoxy species. Infrared spectroscopy clearly shows its presence but also indicates the possible coexistence of a second species. Because of INS spectroscopy’s ability to discriminate between fundamental modes and combinations, we were able to unambiguously show that there is a single intermediate present on the surface of the active catalyst. This work represents a clear example where an understanding of the chemistry at the molecular level can help rationalize improvements in a large scale industrial process with both financial and environmental benefits. <p></p&gt

Inflation, Renormalization, and CMB Anisotropies

In single-field, slow-roll inflationary models, scalar and tensorial (Gaussian) perturbations are both characterized by a zero mean and a non-zero variance. In position space, the corresponding variance of those fields diverges in the ultraviolet. The requirement of a finite variance in position space forces its regularization via quantum field renormalization in an expanding universe. This has an important impact on the predicted scalar and tensorial power spectra for wavelengths that today are at observable scales. In particular, we find a non-trivial change in the consistency condition that relates the tensor-to-scalar ratio "r" to the spectral indices. For instance, an exact scale-invariant tensorial power spectrum, n_t=0, is now compatible with a non-zero ratio r= 0.12 +/- 0.06, which is forbidden by the standard prediction (r=-8n_t). Forthcoming observations of the influence of relic gravitational waves on the CMB will offer a non-trivial test of the new predictions.Comment: 4 pages, jpconf.cls, to appear in the Proceedings of Spanish Relativity Meeting 2009 (ERE 09), Bilbao (Spain

Non-gaussianities and the Stimulated creation of quanta in the inflationary universe

Cosmological inflation generates a spectrum of density perturbations that can seed the cosmic structures we observe today. These perturbations are usually computed as the result of the gravitationally-induced spontaneous creation of perturbations from an initial vacuum state. In this paper, we compute the perturbations arising from gravitationally-induced stimulated creation when perturbations are already present in the initial state. The effect of these initial perturbations is not diluted by inflation and survives to its end, and beyond. We consider a generic statistical density operator $\rho$ describing an initial mixed state that includes probabilities for nonzero numbers of scalar perturbations to be present at early times during inflation. We analyze the primordial bispectrum for general configurations of the three different momentum vectors in its arguments. We find that the initial presence of quanta can significantly enhance non-gaussianities in the so-called squeezed limit. Our results show that an observation of non-gaussianities in the squeezed limit can occur for single-field inflation when the state in the very early inflationary universe is not the vacuum, but instead contains early-time perturbations. Valuable information about the initial state can then be obtained from observations of those non-gaussianities.Comment: 25 page

Spatial curvature effects on molecular transport by diffusion

For a substance diffusing on a curved surface, we obtain an explicit relation valid for very small values of the time, between the local concentration, the diffusion coefficient, the intrinsic spatial curvature and the time. We recover the known solution of Fick's law of diffusion in the flat space limit. In the biological context, this result would be useful in understanding the variations in the diffusion rates of integral proteins and other molecules on membranes.Comment: 10 page

General Orders, no. 7 (U.S. Army. 19 March 1865)

Order issued concerning the death of Maj. Albert Longwell, Surgeon of 88th O.V.I.https://egrove.olemiss.edu/ciwar_milrec/1082/thumbnail.jp

Asymmetric trehalose analogues to probe disaccharide processing pathways in mycobacteria

The uptake and metabolism of the disaccharide trehalose by Mycobacterium tuberculosis is essential for the virulence of this pathogen. Here we describe the chemoenzymatic synthesis of new azido-functionalised asymmetric trehalose probes that resist degradation by mycobacterial enzymes and are used to probe trehalose processing pathways in mycobacteria

Micro and macro approaches to tough polymers for composites

The progress to date on the development of techniques to toughen continuous thermoplastic composites is summarized. The work, using the approach of toughening the polycarbonate composite matrix with rubber particles, has focused on determining the differences between Double Cantilever Beam (DCB) samples molded inhouse and those molded by NASA. Specifically, an effort was made to account for the differences in fracture toughness observed between the various specimens. In addition, preliminary results of tensile dilatometry tests are described; these tests suggest that processes leading to increased volume and enhanced shear banding are occurring within the rubber toughened system. The results of the effort using another approach, the preparation of random block copolycarbonates, are presented. The synthetic route to these species was modified so that higher molecular weights of these materials can be obtained. In addition, an attempt is being made to determine the exact block length or the number of functional groups in the oligomers since this procedure also should lead to high molecular weight materials. Dynamic mechanical analysis of the copolymer prepared so far indicates that the scale of cooperative molecular motion of the PBA polycarbonate at sub-Tg temperatures is larger than five monomer units. Efforts to find a suitable rubber-toughener for a thermoset system (bismaleimides) is also discussed. Included is a description of the various tougheners intended for use or currently being used

Solar Energy for Heating Farm Structures in Kentucky

This report is intended to summarize the important decisions which must be made by farmers in Kentucky, who are considering the utilization of solar energy for heating farm buildings or drying grain