Selective oxidation of alcohols using octahedral molecular sieves: influence of synthesis method and property–activity relations

Manganese oxides having a tunnel structure (OMS-2) have been utilized as selective catalysts for alcohol oxidation. In this study manganese oxide catalysts were synthesized in different media and modified by exchanging the tunnel cation by H⁺, using acid treatment or exchanging with NH₄⁺ followed by thermolysis. Various alcohol oxidations were performed using these catalysts to ascertain the influence of synthesis method on their activity. A correlation is made between lattice oxygen instability and activity of the catalysts, which indicates involvement of the lattice oxygen in the mechanism. The exchange of the tunnel cation with the smaller H⁺ ions leads to weakening of the Mn–O bond, as verified by temperature programmed desorption (TPD) results. Only the chemisorbed oxygen on the surface (O⁻) and the lattice oxygen in the layers close to the surface is involved in the oxygen transfer during the reaction.     

A Study of Ozone Generation by Negative Corona Discharge Through Different Plasma Chemistry Models

The Steady radial distribution of chemical species in a wire‐to‐cylinder ozone generator filled with pure oxygen has been computed by applying four different plasma chemistry models of increasing complexity. The most complete model considers ten species (e, O₂ ⁺, O₂ ^?, O₃ ^?, O^?, O₂, O₂(¹Δ_g), O₂(¹∑_g ⁺), O and O₃) and 79 reactions, including ionization by electron impact, electron attachment and detachment, electron-ion recombination, charge transfer, etc. The chemical model is coupled with the electrical model through Poisson's equation. The spatially averaged ozone density has been computed as a function of the current intensity and compared with the experimental values obtained by UV spectroscopy.     

Surface chemistry of tribochemical reactions explored in ultrahigh vacuum conditions

The thermal decomposition of model extreme-pressure lubricant additives on clean iron was studied in ultrahigh vacuum conditions using molecular beam strategies. Methylene chloride and chloroform react to deposit a solid film consisting of FeCl₂ and carbon, and evolve only hydrogen into the gas phase. No gas-phase products and less carbon on the surface are detected in the case of carbon tetrachloride. Dimethyl and diethyl disulfide react on clean iron to deposit a saturated sulfur plus carbon layer at low temperatures (∼600 K) and an iron sulfide film onto a Fe + C underlayer at higher temperatures (∼950 K). Methane is the only gas-phase product when dimethyl disulfide reacts with iron. Ethylene and hydrogen are detected when diethyl disulfide is used.     

Biofiltration of toluene in the absence and the presence of ethyl acetate under continuous and intermittent loading

BACKGROUND: Two peat biofilters were used for the removal of toluene from air for one year. One biofilter was fed with pure toluene and the other received 1:1 (by weight) ethyl acetate:toluene mixture. RESULTS: The biofilters were operated under continuous loading: the toluene inlet load (IL) at which 80% removal occurred was 116 g m^?3 h^?1 at 57 s gas residence time. Maximum elimination capacity of 360 g m^?3 h^?1 was obtained at an IL of 745 g m^?3 h^?1. The elimination of toluene was inhibited by the presence of ethyl acetate. Intermittent loading, with pollutants supplied for 16 h/day, 5 days/week, did not significantly affect the removal efficiency (RE). Biomass was fully activated in 2 h after night closures, but 6 h were required to recover RE after weekend closures. Live cell density remained relatively constant over the operational period, while the dead cell fraction increased. Finally, a 15 day starvation period was applied and operation then re‐started. Performance was restored with similar re‐acclimatization period to that after weekend closures, and a reduction in dead cell fraction was observed. CONCLUSION: This study demonstrates the capacity of the system to handle intermittent loading conditions that are common in industrial practices, including long‐term starvation. Copyright © 2008 Society of Chemical Industry     

Inhibition of sulfide on the simultaneous removal of nitrate and p‐cresol by a denitrifying sludge

BACKGROUND: Many industrial discharges, such as those generated from petrochemical refineries, contain large amounts of sulfurous, nitrogenous and organic contaminants. Denitrification has emerged as a suitable technology for the simultaneous removal of these pollutants in a single reactor unit; however, more evidence is demanded to clarify the limitations of denitrification on the simultaneous removal of sulfide and phenolic contaminants and to optimize the biological process. The aim of this study was to evaluate the capacity of a denitrifying sludge to simultaneously convert sulfide and p‐cresol via denitrification. RESULTS: Sulfide was the preferred electron donor over p‐cresol, imposing a 5 h lag phase (required for complete sulfide removal) on organotrophic denitrification. Addition of sulfide (20 mg S^2? L^?1) to p‐cresol‐amended denitrifying cultures also decreased the reduction rate of nitrate and nitrite, as well as the production rate of nitrogen gas. Nitrite reduction rate was the most affected step by sulfide, decreasing from 35 to 21 mg N (g VSS d)^?1. A synergistic inhibitory effect of nitrate and sulfide was also observed on nitrite reduction. Despite the effects of sulfide on the respiratory rates monitored, complete removal of nitrate, sulfide and p‐cresol could be achieved after 48 h of incubation. CONCLUSION: Our results suggest that simultaneous removal of sulfide and p‐cresol could be achieved in denitrifying reactors, but a large hydraulic residence time may be required to sustain an efficient process due to inhibitory effects of sulfide. Copyright © 2008 Society of Chemical Industry     

Nonparametric Analysis of the Order-Statistic Model in Software Reliability

In the literature on statistical inference in software reliability, the assumptions of parametric models and random sampling of bugs have been pervasive. We argue that both assumptions are problematic, the first because of robustness concerns and the second due to logical and practical difficulties. These considerations motivate the approach taken in this paper. We propose a nonparametric software reliability model based on the order-statistic paradigm. The objective of the work is to estimate, from data on discovery times observed within a type I censoring framework, both the underlying distribution F from which discovery times are generated and N, the unknown number of bugs in the software. The estimates are used to predict the next time to failure. The approach makes use of Bayesian nonparametric inference methods, in particular, the beta-Stacy process. The proposed methodology is illustrated on both real and simulated data     

Twenty-five years of natural coordinates

In the early eighties, the author and co-workers created and further developed the natural coordinates to describe the motion of 2-D and 3-D multibody systems. Natural coordinates do not need angles or angular parameters to define orientation, leading to constant inertia matrices and to the simplest form of the constraint equations. Natural coordinates are composed by the Cartesian coordinates of some points and the Cartesian components of some unit vectors distributed on the different bodies of the system. The points and vectors can be located in the joints, being shared by contiguous bodies, decreasing or even eliminating the need to set joint constraints and reducing the total number of variables. However, other authors prefer not to share variables in order to get even simpler equations and to keep a bigger decoupling of equations, which is preferable in some cases. In this paper the history of natural coordinates is reviewed, as well as the main contributions coming from other research groups. In the second part of the paper some application areas in which natural coordinates can be particularly advantageous are examined. Commemorative Contribution.     

Mapping of Trellises Associated with General Encoders onto High-Performance VLSI Architectures

A rate 1/n binary generic convolutional encoder is a shift-register circuit where the inputs are information bits and the outputs are blocks of n bits generated as linear combinations on the appropriate shift register contents. The decoding of the outputs of a convolutional encoder can be carried out by the well-known Viterbi algorithm. The communication pattern of the Viterbi Algorithm is given as a graph, called trellis, associated to the state diagram of the corresponding encoder. In this paper we present a methodology that permits the efficient mapping of the Viterbi algorithm onto a column of an arbitrary number of processors. This is done through the representation of the data flow by using mathematical operators which present an inmediate hardware projection. A single operator string has been obtained to represent a generic encoder through the study of the data flow of free-forward encoders and feed-back encoders. The formal model developed is employed for the partitioning of the computations among an arbitrary number of processors in such a way that the data are recirculated opimizing the use of the processors and the communications. As a result, we obtain a highly regular and modular architecture suitable for VLSI implementation.     

An adaptive tracking algorithm for direction finding and array shape estimation in a nonstationary environment

This paper presents an adaptive tracking algorithm for the subspace-based direction of arrival estimation of multiple sources in a nonstationary, environment. The nonstationarities are due to moving sources or to timevarying distortions of the sensor array shape. The proposed algorithm relies on the properties of a linear operator, referred to as the Propagator, which only exploits the linear independency of the source steering vectors. The Propagator allows not only the calibration of the array shape, but also the determination of the source and the noise subspaces without any eigendecomposition of the cross-spectral matrix of the received signals. A gradientbased adaptive algorithm is here proposed for the on-line estimation of the Propagator. A theoretical analysis of the behaviour of this algorithm in a nonstationary environment is given. Simulations are carried out in the case of moving sources and in the case of a time-varying array shape. They exhibit the good performances of the proposed algorithm.     

Using simulation‐based experiments for software requirements engineering

We describe the use of simulation‐based experiments to assess the computer support needs of automation supervisors in the United States Postal Service (USPS). Because of the high cost of the proposed system, the inability of supervisors to articulate their computer support needs, and the infeasibility of direct experimentation in the actual work environment, we used a simulation to study end‐user decision making, and to experiment with alternative computer support capabilities. In Phase One we investigated differences between expert and novice information search and decision strategies in the existing work environment. In Phase Two, we tested the impact of computer support features on performance. The empirical results of the two experiments showed how to differentially support experts and novices, and the effectiveness of proposed information systems before they were built. The paper concludes by examining the implications of the project for the software requirements engineering community.