In situ ESR of CrH-ZSM-5 up to 500°C in flowing gas containing O2, H2O,CCl4, NO,NO2, and C3H6

A flow cell was used for the in situ ESR monitoring of the state and reactivity of chromium ions in Cr-ZSM-5. Calcination of Cr(NO₃)₃/NH₄-ZSM-5 in air at 500°C is accompanied by migration of chromium ions inside the zeolitic channels and stabilization ofisolated Cr⁵⁺ cations near lattice A1³⁺ ions. Calcination of Cr-ZSM-5 at 750°C leads to a gradual disappearance of the isolated Cr⁵⁺ cations and formation of -Cr₂O₃ microcrystals. All the Cr⁵⁺ cations are accessible to gas-phase molecules: O₂ strongly broadens the dipole-dipole signal; H₂O sorption increases the local crystal field symmetry; admission of CCl₄ results in a small change of the Cr⁵⁺ local coordination; strongly stabilized complexes on Cr-ZSM-5 are observed upon sorption of either NO or NO₂. The sorption of C₂H₆ on Cr-ZSM-5 at 20°C is accompanied by a gradual reduction of the Cr⁵⁺ sites. At 500°C in [C₃H₆ + O₂ + He] flow, even at a large excess of oxidant, the reduction of a noticeable part of Cr⁵⁺ ions takes place. At 400°C, in the same gas mixtures, a deeper reduction of Cr⁵⁺ occurs. Closer to stoichiometric conditions, in a [C₃H₆ + NO + He] flow with 120% excess of oxidant the Cr⁵⁺ is completely reduced at 500°C. The oxidation of propene is accompanied by coke deposition on the surface of the catalyst. The implications of the results are discussed.     

Reduction of NO by H2 on PdO-MoO3/γ-Al2O3 of low molybdena loading

The catalytic activity and selectivity of three PdO-MoO₃/-Al₂O₃ catalysts containing about 2% Pd and 2% Mo were studied for the reduction of NO by h₂ in the presence of varying amounts of oxygen at temperatures from 50 to 550 °C. The results are compared with those for PdO/-Al₂O₃, PdO-MoO₃/-Al₂O₃ containing 2% Pd and 20% Mo, and a commercial Pt-Rh catalyst. In the absence of oxygen, the conversion of NO to N₂ and N₂O is higher on the three catalysts than it is on PdO/-Al₂O₃ at 500 and 550 °C. In the presence of oxygen, the yields of N₂ and N₂O are generally lower on two of the PdO-MoO₃/-Al₂O₃ catalysts than on PdO/-Al₂O₃.     

Uniform strength for large deflections of cantilever beams under end point load

Analysis is conducted for slender beams with a varying cross-section under large non-linear elastic deformation. A thickness variation function is derived to achieve optimal - constant maximum bending stress distribution along the beam for inclined end load of arbitrary direction. Closed form solutions are derived for the large deflections that correspond to the various loading conditions. The analysis is repeated for a beam with optimally varying width (for arbitrary end force) and the width variation function is also determined.     

Recent results on Nova

On the Nova Laser at LLNL, we have recently demonstrated many of the key elements required for assuring that the next proposed laser, the National Ignition Facility (NIF) will reach ignition. In particular, we have achieved a drive of 300 eV in laser heated hohlraums; have shown good understanding and control of symmetry in hohlruams; created large NIF-Scale plasmas with plasma and irradiation conditions relevant to NIF targets that showed low levels of plasma instabilities; demonstrated a good understanding of hydrodynamic instability and subsequent pusher/fuel mix in implosions by means of spectroscopic tracers; and performed integrated implosion experiments that have performed well even under stringent convergences of order 25, which is well into the NIF ignition target regime.     

Decomposition of nitric oxide and its reduction by CO over superconducting and related cuprate catalysts

Catalytic activities of five non-conducting and three superconducting cuprates were measured for the decomposition of NO and the reduction of NO by CO. The concentration of the reactants and the space velocities approximate the conditions of automotive catalysts. In contrast to earlier results, obtained at 20 to 30 times higher partial pressures of NO and 20 to 100 times lower space velocities, none of the catalysts, including five perovskite-like cuprates, showed significant activity for the decomposition of NO at reaction temperatures up to 700 °C. All catalysts were fairly active for the reduction of NO. At temperatures above about 400 °C on the perovskite-like cuprates YBa₂Cu₃O_7-x and Ba₂CuO_3.5-x , the rates for NO reduction were higher than on CuO. All catalysts lost activity for NO reduction in the presence of oxygen (oxidizing conditions).     

Effects of calcium,strontium, and barium as catalysts and sulphur scavengers in the steam gasification of coal chars

Effects of alkaline earths on the steam gasification of two coal chars, one of low and one of high intrinsic reactivity, were evaluated gravimetrically. The chars were derived from coal powders which had been impregnated with Ca, Sr, or Ba, pelletized, and pyrolysed in nitrogen. The additives increased the gasification rates in the order Ca < Sr < Ba. It follows from reaction kinetics that catalysis is caused by a large increase in the density of reaction sites, not by a lowering of the true activation energy. As shown by electron micrographs and elemental maps obtained by X-ray analysis, the strong catalytic effect is closely associated with the ability of the alkaline-earth species to spread over the char and to preserve contact with a freshly formed carbon surface as the gasification proceeds. The alkaline-earth catalysts are severely poisoned by hydrogen sulphide or sulphur dioxide from an external source.     

Reduction of NO by H2 and CO on PdO-MoO3/γ-Al2O3 of low molybdena loading

The activity and selectivity in the catalytic reduction of NO by a mixture of CO and H₂ of three PdO-MoO₃/-Al₂O₃ catalysts are compared in the presence of varying amounts of oxygen at reaction temperatures from 100 to 550°C. The catalysts were prepared by different methods and contain about 2% Mo and 2% Pd. Results are compared with those for PdO/-Al₂O₃, PdO-MoO₃/-Al₂O₃ containing 2% Pd and 20% Mo, and a commercial Pt-Rh catalyst. The PdO-MoO₃/-Al₂O₃ catalysts are more active for the selective reduction of NO to N₂ and N₂O than PdO/-Al₂O₃ under slightly oxidizing conditions at temperatures from 300 to 550°C. At these reaction conditions, the fresh PdO-MoO₃/-Al₂O₃ catalysts are comparable with a commercial Pt-Rh catalyst. The improved activity of PdO-MoO₃/-Al₂O₃ relative to PdO/-Al₂O₃ is believed to be due to the interaction between Pd and Mo. The effect of O₂ on the activity and selectivity of these catalysts is different in the reduction of NO by H₂, by CO, and by a mixture of H₂ and CO. The results using the mixture of reductants cannot be inferred from the results with the single reductants.     

Exact and approximate solutions of the container ship stowage problem

This paper deals with a stowage plan for containers in a container ship. Containers on board a container ship are placed in stacks, located in many bays. Since the access to the containers is only from the top of the stack, a common situation is that contianers designated for port J must be unloaded and reloaded at port I (before J) in order to access containers below them, designated for port I. This operation is called “shifting”. A container ship calling many ports, may encounter a large number of shifting operations, some of which can be avoided by efficient stowage planning. In general, the stowage plan must also take into account stability and strength requirements, as well as several other constraints on the placement of containers. In this paper we deal with stowage planning in order to minimize the number of shiftings, without considering stability constraints. First, a 0–1 binary linear programming formulating is presented that can find the optimal solution for stowage in a single rectangular bay of a vessel calling a given number of ports, assuming that the number of constainers to ship is known in advance. This model was successfully implemented using the GAMS software system. It was found, however, that finding the optimal solution using this model is quite limited, because of the large number of binary variables needed for the formulation. For this reason, several alternative heuristic algorithms were developed. The one presented here is based on a “reduced” transportation matrix. Containers with the same source and destination ports are stowed in full stacks as much as possible, and only the remaining containers are allocated by the binary linear programming model. This approach often allows the stowage planning of a much larger number of containers than using the exact formulation.     

Mellin transforms and asymptotics

Mellin transforms and Dirichlet series are useful in quantifying periodicity phenomena present in recursive divide-and-conquer algorithms. This note illustrates the techniques by providing a precise analysis of the standard topdown recursive mergesort algorithm, in the average case, as well as in the worst and best cases. It also derives the variance and shows that the cost of mergesort has a Gaussian limiting distribution. The approach is applicable to a number of divide-and-conquer recurrences.