Oxidation of aqueous sulfur dioxide catalyzed by poly-4-vinylpyridine-Cu(II) complex. Part 1: Homogeneous phase oxidation

The oxidation of aqueous sulfur dioxide in the presence of polymer-supported copper(II) catalyst is also accompanied by homogeneous oxidation of aqueous sulfur dioxide catalyzed by leached copper(II) ions. Aqueous phase oxidation of sulfur dioxide of low concentrations by oxygen in the presence of dissolved copper(II) has therefore been studied. The solubility of SO2 in aqueous solutions is not affected by the concentration of copper(II) in the solution. In the oxidation reaction, only HSO3- is the reactive S(IV) species. Based on this observation a rate model which also incorporates the effect of sulfuric acid on the solubility of SO2 is developed. The rate model includes a power-law type term for the rate of homogeneous phase reaction obtained from a proposed free-radical chain mechanism for the oxidation. Experiments are conducted at various levels of concentrations of SO2 and O-2 in the gas phase and Cu(II) in the liquid phase. The observed orders are one in each of O-2, Cu(II) and HSO3-. This suggests a first-order termination of the free radicals of bisulfite ions.

A rapid and highly selective method for the estimation of pyro-,tri- and orthophosphates

A rapid, highly selective and simple method has been developed for the quantitative determination of pyro-, tri- and orthophosphates. The method is based on the formation of a solid complex of bis(ethylenediamine)cobalt(III) species with pyrophosphate at pH 4.2-4.3, with triphosphate at pH 2.0-2.1 and with orthophosphate at pH 8.2-8.6. The proposed method for pyro- and triphosphates differs from the available method, which is based on the formation of an adduct with tris(ethylenediamine)cobalt(III) species. The complexes have the composition [Co(en)(2)HP2O7]4H(2)O and [Co(en)(2)H2P3O10]2H(2)O, respectively. The precipitation is instantaneous and quantitative under the recommended optimum conditions giving 99.5% gravimetric yield in both cases. There is no interferences from orthophosphate, trimetaphosphate and pyrophosphate species in the triphosphate estimation up to 5% of each component. The efficacy of the method has been established by determining pyrophosphate and triphosphate contents in various matrices. In the case of orthophosphate, the proposed method differs from the available methods such as ammonium phosphomolybdate, vanadophosphomolybdate and quinoline phosphomolybdate, which are based on the formation of a precipitate, followed by either titrimetry or gravimetry. The precipitation is instantaneous and the method is simple. Under the recommended pH and other reaction conditions, gravimetric yields of 99.6-100% are obtainable. The method is applicable to orthophosphoric acid and a variety of phosphate salts.

A Simple and Convenient One Step Method for the Reductive Deoxygenation of Aryl Ketones to Hydrocarbons

A one step, clean and efficient, conversion of arylaldehydes, ketones and ketals into the corresponding hydrocarbon using ionic hydrogenation conditions employing sodium cyanoborohydride in the presence of two to three equivalents of BF3. OEt(2) is described.

Homogeneous isotropic turbulence: large momentum expansion

High temperature expansion is an effective tool for studying second order phase transitions. With this in mind, we have looked at a high momentum expansion for homogeneous isotropic turbulence. Combining our results with those of the inertial range, we give another view of extended self-similarity (ESS).

An accurate rating aggregation method for generating item reputation

Many websites presently provide the facility for users to rate items quality based on user opinion. These ratings are used later to produce item reputation scores. The majority of websites apply the mean method to aggregate user ratings. This method is very simple and is not considered as an accurate aggregator. Many methods have been proposed to make aggregators produce more accurate reputation scores. In the majority of proposed methods the authors use extra information about the rating providers or about the context (e.g. time) in which the rating was given. However, this information is not available all the time. In such cases these methods produce reputation scores using the mean method or other alternative simple methods. In this paper, we propose a novel reputation model that generates more accurate item reputation scores based on collected ratings only. Our proposed model embeds statistical data, previously disregarded, of a given rating dataset in order to enhance the accuracy of the generated reputation scores. In more detail, we use the Beta distribution to produce weights for ratings and aggregate ratings using the weighted mean method. Experiments show that the proposed model exhibits performance superior to that of current state-of-the-art models.

On the sensitivity of elastic waves due to structural damages:Time-frequency based indexing method

Time-frequency analysis of various simulated and experimental signals due to elastic wave scattering from damage are performed using wavelet transform (WT) and Hilbert-Huang transform (HHT) and their performances are compared in context of quantifying the damages. Spectral finite element method is employed for numerical simulation of wave scattering. An analytical study is carried out to study the effects of higher-order damage parameters on the reflected wave from a damage. Based on this study, error bounds are computed for the signals in the spectral and also on the time-frequency domains. It is shown how such an error bound can provide all estimate of error in the modelling of wave propagation in structure with damage. Measures of damage based on WT and HHT is derived to quantify the damage information hidden in the signal. The aim of this study is to obtain detailed insights into the problem of (1) identifying localised damages (2) dispersion of multifrequency non-stationary signals after they interact with various types of damage and (3) quantifying the damages. Sensitivity analysis of the signal due to scattered wave based on time-frequency representation helps to correlate the variation of damage index measures with respect to the damage parameters like damage size and material degradation factors.

Axially homogeneous, zero mean flow buoyancy-driven turbulence in a vertical pipe

We report an experimental study of a new type of turbulent flow that is driven purely by buoyancy. The flow is due to an unstable density difference, created using brine and water, across the ends of a long (length/diameter = 9) vertical pipe. The Schmidt number Sc is 670, and the Rayleigh number (Ra) based on the density gradient and diameter is about 10(8). Under these conditions the convection is turbulent, and the time-averaged velocity at any point is `zero'. The Reynolds number based on the Taylor microscale, Re-lambda, is about 65. The pipe is long enough for there to be an axially homogeneous region, with a linear density gradient, about 6-7 diameters long in the midlength of the pipe. In the absence of a mean flow and, therefore, mean shear, turbulence is sustained just by buoyancy. The flow can be thus considered to be an axially homogeneous turbulent natural convection driven by a constant (unstable) density gradient. We characterize the flow using flow visualization and particle image velocimetry (PIV). Measurements show that the mean velocities and the Reynolds shear stresses are zero across the cross-section; the root mean squared (r.m.s.) of the vertical velocity is larger than those of the lateral velocities (by about one and half times at the pipe axis). We identify some features of the turbulent flow using velocity correlation maps and the probability density functions of velocities and velocity differences. The flow away from the wall, affected mainly by buoyancy, consists of vertically moving fluid masses continually colliding and interacting, while the flow near the wall appears similar to that in wall-bound shear-free turbulence. The turbulence is anisotropic, with the anisotropy increasing to large values as the wall is approached. A mixing length model with the diameter of the pipe as the length scale predicts well the scalings for velocity fluctuations and the flux. This model implies that the Nusselt number would scale as (RaSc1/2)-Sc-1/2, and the Reynolds number would scale as (RaSc-1/2)-Sc-1/2. The velocity and the flux measurements appear to be consistent with the Ra-1/2 scaling, although it must be pointed out that the Rayleigh number range was less than 10. The Schmidt number was not varied to check the Sc scaling. The fluxes and the Reynolds numbers obtained in the present configuration are Much higher compared to what would be obtained in Rayleigh-Benard (R-B) convection for similar density differences.

Simple Method of Preparing Graphene Flakes by an Arc-Discharge Method

Arc discharge between graphite electrodes under a relatively high pressure of hydrogen yields graphene flakes generally containing 2-4 layers in the inner wall region of the arc chamber. The graphene flakes so obtained have been characterized by X-ray diffraction, atomic force microscopy, transmission electron microscopy, and Raman spectroscopy. The method is eminently suited to dope graphene with boron and nitrogen by carrying out arc discharge in the presence of diborane and pyridine respectively.

Prop-2-ynyl as a protective group for carboxylic acids: A mild method for the highly selective deprotection of prop-2-ynyl esters using tetrathiomolybdate

It is shown that prop-2-ynyl esters are useful protecting groups for carboxylic acids and that they are selectively deprotected in the presence of other esters on treatment with tetrathiomolybdate under mild conditions.

Influence of road traffic environment and mobile phone distraction on the speed selection behaviour of young drivers

Travel speed is one of the most critical parameters for road safety; the evidence suggests that increased vehicle speed is associated with higher crash risk and injury severity. Both naturalistic and simulator studies have reported that drivers distracted by a mobile phone select a lower driving speed. Speed decrements have been argued to be a risk compensatory behaviour of distracted drivers. Nonetheless, the extent and circumstances of the speed change among distracted drivers are still not known very well. As such, the primary objective of this study was to investigate patterns of speed variation in relation to contextual factors and distraction. Using the CARRS-Q high-fidelity Advanced Driving Simulator, the speed selection behaviour of 32 drivers aged 18-26 years was examined in two phone conditions: baseline (no phone conversation) and handheld phone operation. The simulator driving route contained five different types of road traffic complexities, including one road section with a horizontal S curve, one horizontal S curve with adjacent traffic, one straight segment of suburban road without traffic, one straight segment of suburban road with traffic interactions, and one road segment in a city environment. Speed deviations from the posted speed limit were analysed using Ward’s Hierarchical Clustering method to identify the effects of road traffic environment and cognitive distraction. The speed deviations along curved road sections formed two different clusters for the two phone conditions, implying that distracted drivers adopt a different strategy for selecting driving speed in a complex driving situation. In particular, distracted drivers selected a lower speed while driving along a horizontal curve. The speed deviation along the city road segment and other straight road segments grouped into a different cluster, and the deviations were not significantly different across phone conditions, suggesting a negligible effect of distraction on speed selection along these road sections. Future research should focus on developing a risk compensation model to explain the relationship between road traffic complexity and distraction.

A three-dimensional hybrid smoothed finite element method (H-SFEM) for nonlinear solid mechanics problems

This paper presents a novel three-dimensional hybrid smoothed finite element method (H-SFEM) for solid mechanics problems. In 3D H-SFEM, the strain field is assumed to be the weighted average between compatible strains from the finite element method (FEM) and smoothed strains from the node-based smoothed FEM with a parameter α equipped into H-SFEM. By adjusting α, the upper and lower bound solutions in the strain energy norm and eigenfrequencies can always be obtained. The optimized α value in 3D H-SFEM using a tetrahedron mesh possesses a close-to-exact stiffness of the continuous system, and produces ultra-accurate solutions in terms of displacement, strain energy and eigenfrequencies in the linear and nonlinear problems. The novel domain-based selective scheme is proposed leading to a combined selective H-SFEM model that is immune from volumetric locking and hence works well for nearly incompressible materials. The proposed 3D H-SFEM is an innovative and unique numerical method with its distinct features, which has great potential in the successful application for solid mechanics problems.

Spatial Variability of the Depth of Weathered and Engineering Bedrock using Multichannel Analysis of Surface Wave Method

In this paper an attempt has been made to evaluate the spatial variability of the depth of weathered and engineering bedrock in Bangalore, south India using Multichannel Analysis of Surface Wave (MASW) survey. One-dimensional MASW survey has been carried out at 58 locations and shear-wave velocities are measured. Using velocity profiles, the depth of weathered rock and engineering rock surface levels has been determined. Based on the literature, shear-wave velocity of 330 ± 30 m/s for weathered rock or soft rock and 760 ± 60 m/s for engineering rock or hard rock has been considered. Depths corresponding to these velocity ranges are evaluated with respect to ground contour levels and top surface levels have been mapped with an interpolation technique using natural neighborhood. The depth of weathered rock varies from 1 m to about 21 m. In 58 testing locations, only 42 locations reached the depths which have a shear-wave velocity of more than 760 ± 60 m/s. The depth of engineering rock is evaluated from these data and it varies from 1 m to about 50 m. Further, these rock depths have been compared with a subsurface profile obtained from a two-dimensional (2-D) MASW survey at 20 locations and a few selected available bore logs from the deep geotechnical boreholes.

Denoising neural data with state-space smoothing: Method and application

Neural data are inevitably contaminated by noise. When such noisy data are subjected to statistical analysis, misleading conclusions can be reached. Here we attempt to address this problem by applying a state-space smoothing method, based on the combined use of the Kalman filter theory and the Expectation–Maximization algorithm, to denoise two datasets of local field potentials recorded from monkeys performing a visuomotor task. For the first dataset, it was found that the analysis of the high gamma band (60–90 Hz) neural activity in the prefrontal cortex is highly susceptible to the effect of noise, and denoising leads to markedly improved results that were physiologically interpretable. For the second dataset, Granger causality between primary motor and primary somatosensory cortices was not consistent across two monkeys and the effect of noise was suspected. After denoising, the discrepancy between the two subjects was significantly reduced.

A Classification of Homogeneous Operators in the Cowen-Douglas Class

A complete list of homogeneous operators in the Cowen-Douglas class B-n(D) is given. This classification is obtained from an explicit realization of all the homogeneous Hermitian holomorphic vector bundles on the unit disc under the action of the universal covering group of the bi-holomorphic automorphism group of the unit disc.

A new method for the in vivo identification of mechanical properties in arteries from cine MRI images: Theoretical framework and validation

Quantifying the stiffness properties of soft tissues is essential for the diagnosis of many cardiovascular diseases such as atherosclerosis. In these pathologies it is widely agreed that the arterial wall stiffness is an indicator of vulnerability. The present paper focuses on the carotid artery and proposes a new inversion methodology for deriving the stiffness properties of the wall from cine-MRI (magnetic resonance imaging) data. We address this problem by setting-up a cost function defined as the distance between the modeled pixel signals and the measured ones. Minimizing this cost function yields the unknown stiffness properties of both the arterial wall and the surrounding tissues. The sensitivity of the identified properties to various sources of uncertainty is studied. Validation of the method is performed on a rubber phantom. The elastic modulus identified using the developed methodology lies within a mean error of 9.6%. It is then applied to two young healthy subjects as a proof of practical feasibility, with identified values of 625 kPa and 587 kPa for one of the carotid of each subject.