The wall-jet electrode and the study of electrode reaction mechanisms: the EC reaction

The theory of EC reactions at a wall-jet electrode is developed using a computational procedure based on the Backwards Implicit Method. In particular, for the case of a reversible electron transfer, it is shown that the variation of the halfwave potential with solution flow rate provides a means of characterizing the EC mechanism. A working curve is presented which permits the analysis of experimental data and the deduction of the rate constant for the following chemical reaction.Nomenclature a diameter of the jet - a _j matrix element (j = 2,3,..., ) - b _j matrix element (j = 1,2,..., ) - C _j matrix element (j = 1,2,..., ) - D diffusion coefficient - d _j vector element (j = 1,2,..., ) - E electrode potential - E ⁰ standard electrode potential of A/B couple - F Faraday constant - g(A) normalized concentration of A - g(B) normalized concentration of B - I current - I _LIM transport limited curren - J number of points inr-direction on finite difference grid - j conter,j=1, 2,...,J - K Number of points inz-direction on finite difference grid - K _j,k+1 normalized rate constant (Equation 23) - k counter,k=1, 2,...,K - k counter,k=1, 2,...,K - k _c experimental constant - first order rate constant - M constant defined byM =k _c ⁴ V _f ³ /2³a² - R electrode radius - r radial coordinate - u _j vector element (j = 1,2,..., ) - V volume flow rate (cm³ s^–1) - _r solution velocity inr-direction - _z solution velocity inz-direction - z coordinate normal to electrode surface - dimensionless distance parameter (see Equation 5) - dimensionless variable (Equation 25) - normalized electrode potential - _1/2 normalized halfwave potential - kinematic viscosity (cm² s^–1) - dimensionless variable (Equation 26) - {d} _k vector{d _1,k ,d _2,k ,...d _j–1,k} - {u} _k vector {u _1,k+1,u _2,k+1,...,u _j–1,k+1}     

Reliability Analysis Applied on Land Subsidence Effects of Groundwater Remediation: Probabilistic vs. Deterministic Approach

The quantification of soil variability is one of the most important aspects in the geo-engineering context. The uncertainty analysis is the main part of the reliability assessment for which a quantitative evaluation was performed in this study. The Reliability Index and the Probability of Failure using the First-Order Reliability Method (FORM) represents both, an effective method which is easy to implement at the same time. This work analyzes possible effects of compaction induced into the aquifer of the Scarlino Plain, caused by the extension of the hydraulic barrier for groundwater remediation. The currently implemented vertical barrier is composed of 12 wells which reach the depth of 10 m. The improvement of the project involves the construction of a further 40 clusters, each consisting of a doublet which intercepts different depths (10 and 18 m). The models of the subsoil stratigraphy and of the groundwater were built using a numerical model. The groundwater flow and the piezometric surface in the current configuration of the barrier were studied and the project configuration was evaluated. Using the Aquitard drainage model, the land subsidence was estimated to calculate the maximum admissible displacement related to exhibited goods, the so called territorial vulnerability. The evaluation analysis was performed using a traditional deterministic approach, followed by a reliability method based on probabilistic models. Finally, the respective results were reported in a soil mapping with overlapping layers.     

Evaluation of hydraulic excavator Human–Machine Interface concepts using NASA TLX

This study evaluated newly proposed Human–Machine Interface (HMI) design concepts for improving the ergonomics of hydraulic excavators. The design concepts were based on an augmented interaction technique which involved the use of heads-up display (HUD) and coordinated control as HMI elements. Two alternative HMI designs were elaborated in order to separately evaluate the ergonomic impacts of the head-up display and the coordinated control by comparing them to the standard HMI design. The effectiveness of these three HMI designs in terms of the reduction of the operators' mental and physical workload were assessed by conducting experiments utilizing human subjects, ages 23–35 years. The National Aeronautics and Space Administration's Task Load Index (NASA TLX) method was used for collecting subjective workload scores based on a weighted average of ratings of six factors: Mental Demand, Physical Demand, Temporal Demand, Own Performance, Effort, and Frustration Level. The results showed that the type of HMI design affects different aspects of the operator's workload. Indeed, it showed how the proposed augmented interaction is an effective solution for reducing the ergonomic gaps in terms of mental workload, and to a lesser extent the physical workload, subjected by the standard HMI design.     

Information Sharing Among Disaster Responders - An Interactive Spreadsheet-Based Collaboration Approach

Recent natural disasters have led crisis management organizations to revise their protocols so as to rely on the contribution of a wider range of actors, including simple citizens as well as expert operators, to support decision making activities. Reliable and timely information sharing among members of distributed teams of disaster responders has become paramount for the success of the overall crisis management process. In this paper we propose a crisis management system based on spreadsheet-mediated collaboration among on-site responders and decision makers. To share data a common spreadsheet artifact has been developed by using a participatory design approach which is accessed through mobile user interfaces. The evaluation results showed that the use of the spreadsheet artifact has resulted in more effective decision making relating to set of earthquake management scenarios in high-risk areas located in Italy.     

Methanol oxidation on Au/TiO2 catalysts

We have investigated the adsorption and reaction of methanol with Au/TiO₂ catalysts using a pulsed flow reactor, DRIFTS and TPD. The TiO₂ (P25) surface adsorbed a full monolayer of methanol, much of it in a dissociative manner, forming methoxy groups associated with the cationic sites, and hydroxyl groups at the anions. The methoxy is relatively stable until 250 °C, at which point decomposition occurs, producing mainly dimethyl ether by a bimolecular surface reaction. As the concentration of methoxy on the surface diminishes, so the mechanism reverts to a de-oxygenation pathway, producing mainly methane and water (at ~330 °C in TPD), but also with some coincident CO and hydrogen. Au catalysts were prepared by the deposition-precipitation method to give Au loadings between 0.5–3 wt %. The effect of low levels of Au on the reactivity is marked. The pathway which gives methane, which is characteristic of titania, remains, but a new feature of the reaction is the evolution of CO₂ and H₂ at lower temperature (a peak is seen in TPD at 220 °C), and the elimination of the DME-producing state. Clearly this is associated with the presence of Au and appears to be due to the production of a formate species on the surface of the Au component. This formate species is mainly involved in the reaction of methanol with the Au/TiO₂ catalysts which results in a combustion pathway being followed, with complete conversion occurring by ~130 °C.     

Surface properties of fluorinated hybrid coatings

A commercial perfluoropolyether containing alkoxysilane functionalities was employed to prepare organic–inorganic hybrid coatings by using the sol‐gel process in the presence of tetraethoxysilane. Contact angle analysis revealed a strong hydrophobic and oleophobic character of the coatings almost independently from the molecular weight of the starting fluorinated oligomer. Surface tension values were in the range of 14–16 mN/m, suggesting a preferential segregation of fluorinated segments onto the surface of the coating. Atomic force microscopy showed the presence very smooth surfaces permitting to neglect the contribution of the surface roughness to wettability. Friction coefficient values were markedly lower with respect to the value of uncoated glass substrate. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1483–1488, 2006     

A second-generation system for unbiased reading frame selection

Reading frame selection of nucleic acids has important implications for protein engineering and genomics. Current methods are limited because selection of the gene of interest inevitably depends on the solubility of its translated product. Here we report the construction of the pInSALect vector, which provides strict reading frame selection without concomitant selection for protein solubility or folding. This plasmid incorporates the cis-splicing VMA intein sequence from Saccharomyces cerevisiae to facilitate the post-translational self-excision of the protein of interest, thereby eliminating potential aggregation problems. Results from two libraries of chimeric glycinamide ribonucleotide formyltransferases confirm the superior performance of pInSALect over existing reading frame selection systems.     

Catalyst fragmentation during propylene polymerization: Part I. The effects of grain size and structure

Fragmentation of support/catalyst particles during propylene polymerization in the gas phase is analyzed via a mathematical model including energy and mass transfer with chemical reaction processes. The rupture phenomenon is considered specifically by the model, and evaluated as it proceeds in time, Two different regions are recognized in the polymerizing particle at fragmentation time: an inner core resembling the original solid support/catalyst structure, and an external set of layers where most of the polymerization occurs. Model predictions concerning the effects of fragmentation on polymerization are discussed. The influence of different degrees of fragmentation on thermal runaways and monomer availability at active sites located inside the support/catalyst/polymer complex is shown. Monomer concentration profiles inside the growing particles are explained in terms of the combined fragmentation-polymerization interaction. Results show a strong influence of catalyst structure on critical phenomena during early polymerization stages, and suggest the possibility of controlling critical parameters via the definition of fragment structure at catalyst preparation time.     

Effect of Residual Surface Stress on the Strenght Distribution of Brittle Materials

The introduction of residual surface stresses into a material can change the strength distribution simply due to variability in the stress intensity factor of surface cracks. This variability arises from the distribution in surface (critical) crack lengths. A fracture mechanics approach was used to determine the influence of surface compression on the average strength and the standard deviation of the strength distribution. The strengths of the stress-free samples were assumed to fit a twoparameter Weibull distribution, and the increases in strength resulting from the surface compression were determined using fracture mechanics. It was determined from the analysis that the standard deviation/average strength ratio (coefficient of variation) initially increases, passes through a maximum, and ultimately reaches a plateau value below the initial value, as one increases the depth of surface compression. The maximum increase in the strength scatter occurs when the depth of the surface compression is approximately equal to the characteristic crack size. These changes were found to be dependent on the magnitude of the surface stress, as well as the characteristic strength, Weibull modulus, and fracture toughness of the stress-free material.     

Estimation of lamb carcass composition from measurements of the speed of ultrasound in the soft tissues of live animals and carcasses

The application of the velocity of sound (VOS) technique to lamb carcasses in a previous study (Fisher & Page, 1986) measured composition at a hind limb and neck site but was not as precise as fat scores in predicting lean proportion. This study examines VOS measurements made at sites in the hind limbs and along the vertebral column in live sheep and carcasses. A group (A) comprising five breeds of males and females (n = 61) and a sub-group (B) of Scottish Blackface castrated males (n = 34) were studied, and the reciprocal velocity of ultrasound (RV) was measured on the live sheep immediately behind the shoulder and over the last rib using a fixed-distance transducer assembly operating at 5 MHz, and in the hind limbs at 2·25 MHz using the apparatus described by Miles et al. (1984). Corresponding measurements were made on the carcasses which were classified by a Meat and Livestock Commission fatstock officer and then dissected. Standard deviations of lean proportion were 4·48% (A) and 3·39% (B). The residual standard deviations (rsds) for groups A and B respectively were obtained using the following predictors: live mass (LM) 4·27% and 2·96%; LM + breed (B) 3·08% (group A only); LM + mean RV 2·36% and 2·07%; LM + B + mean RV 1·99% (group A only). Using carcass measurements: carcass mass (CM) 4·25% and 2·90%; CM + MLC fat score 2·99% and 2·12%; CM + RV last rib 2·89% and 2·02%. These data show that VOS measurements through dorsal sites of live sheep provide encouragingly precise estimates of carcass lean proportion. For carcasses, dorsal sites provide a less precise estimate of carcass lean but when carcass mass is included in multiple regression the precision of the correlation is comparable with that of multiple regression of fat score with carcass mass.