EPR Study of CO Adsorption onto CoZSM-5 Zeolite: Evidence for Spin Crossover upon Coordination and |z2, 2A1〉 Ground State

Adsorption of CO onto dehydrated cobalt-exchanged ZSM-5 zeolite was studied by CW-EPR techniques. It is shown that the reversible formation of a low spin carbonyl ¹{Co(CO) _n }⁷ adduct upon addition of carbon monoxide at p _CO>50–60 Torr involves significant change in the spin state of Co²⁺ from S=3/2 to 1/2. The spin Hamiltonian parameters of the adduct g _x =2.222, g _y =2.184, g _z =2.011, |A _x |=3.8 mT, |A _y |=3.2 mT, |A _z |=7.9 mT were determined by a computer simulation and further discussed in terms of the possible ground state and molecular structure. It is shown that the ¹{Co(CO) _n }⁷ cage complex exhibits a C_2v symmetry with |z ²,²A₁ ground state.     

Influence of operation parameters on the separation of mixtures by pervaporation and vapor permeation with inorganic membranes. Part 1: Dehydration of solvents

The separation performance of two different commercially available tubular inorganic membranes was studied for solvent dehydration. The separation layers consisted of A-type zeolite and microporous silica. The membrane characteristics were determined as function of operating conditions such as feed composition, temperature, and permeate pressure in pervaporation and vapor permeation. Among different membranes of the same batch, flux and selectivity were reproducible within 10%. The partial flux of water as the preferentially permeating component increases linearly with the water vapor pressure difference between feed and permeate and depends only marginally (viscosity influence) upon the properties of the organic component. The flux of the organic (retained) component is low and can best be described by assuming a substance and membrane specific permeance (flux over partial pressure difference) that is independent of composition. At very low water concentration in the feed one would expect a strong increase in permeability of the retained component through non-zeolite pores and larger silica pores as predicted by pure component measurements. However, this effect was not observed in mixtures within the concentration range studied here. A temperature rise improves flux rates exponentially while selectivity remains high. Thus, higher module cost in comparison to polymeric membranes can be compensated by reduced membrane area if a higher operating temperature can be chosen. Flux and selectivity decline as a function of permeate pressure with decreasing driving force. In vapor permeation with inorganic membranes superheating of the vaporous feed improves their performance while for polymeric materials a steep flux decline is observed. High flux and selectivity are obtained in the separation of water from alcohols. The normalized flux values of the A-type zeolite membrane are roughly 10 kg/m² h bar with a mixture selectivity of 2000 for methanol, 4000 for ethanol and 8000 for n-butanol. The average permeance of the amorphous silica membrane lies above 12 kg/m² h bar with mixture selectivity of 50 for methanol, 500 for ethanol and 2000 for n-butanol. The separation mechanism is mainly based on adsorption and diffusion enhanced by shape selectivity and size exclusion in some cases. The transport characteristics could be described with a simple transport model based on normalized permeate fluxes. With regard to the operation stability of the membranes, no deterioration of the performance was observed for the A-type zeolite in solvent dehydration or in separation of water from reaction mixtures. The silica membrane showed an initial conditioning effect involving a rearrangement of Si-OH groups with an increase in selectivity and decrease in flux of about 30%. After a few hours the performance stabilized and remained constant during further operation.     

Observation of single-walled carbon nanotubes by photoemission microscopy

Single-walled carbon nanotube networks grown on SiO₂ pillars were studied by means of scanning photoemission microscopy. The individual nanotubes or nanotube bundles growing from the pillar tops were observed in C 1s images. Band bending near catalytic Fe/nanotube contacts in an end-bonded configuration was studied by measuring C 1s spectra along the tube axes. Within our experimental resolution, no band bending was observed. This implies that the depletion width is less than the spatial resolution of the scanning photoemission microscope (90 nm) or that the amount of the band bending is less than 0.1 eV.     

Comparing global land-cover products – implications for geoscience applications: an investigation for the trans-boundary Mekong Basin

In this article we present the results of a comparison of six globally available land-cover products for the Mekong Basin – an area that spans 795,000 km² and comprises parts of six riparian countries: China, Myanmar, Thailand, Laos, Cambodia, and Vietnam. The basin covers most climatic zones: from high-altitude, snow-covered mountainous regions in the north, to subtropical and tropical rainforest areas and agricultural land further south. The geopolitically important region not only is home to over 72,000,000 inhabitants, but also is a centre of attention of several environmental modelling experts, trying to assess future hydrologic dynamics, climate variability, as well probable land-use developments in the area.

We compare land-cover products of the University of Maryland, UMD 1992–1993, the GLC 2000 product, the GlobCover products of 2004–2006 and 2009, as well as the MODIS-derived land-cover products of 2001 and 2009. For harmonization of individual legends, the Land Cover Classification System, LCCS, has been employed. However, even after harmonization, cross-tabulation among the products reveals extreme differences, where the impact of differing classification algorithms weighs higher than the impact of temporal coincidence of products. Especially, differences within mixed-vegetation classes are large, strongly impacting the overall assessment of forested land, other vegetated land, and even cultivated land in the Mekong Basin. The findings presented here are of high relevance for the modelling community as well as Mekong-related environmental studies, which should consider global remote-sensing-derived products with caution and solid background knowledge.     

Continuous Levels‐of‐Detail and Visual Abstraction for Seamless Molecular Visualization

Molecular visualization is often challenged with rendering of large molecular structures in real time. We introduce a novel approach that enables us to show even large protein complexes. Our method is based on the level‐of‐detail concept, where we exploit three different abstractions combined in one visualization. Firstly, molecular surface abstraction exploits three different surfaces, solvent‐excluded surface (SES), Gaussian kernels and van der Waals spheres, combined as one surface by linear interpolation. Secondly, we introduce three shading abstraction levels and a method for creating seamless transitions between these representations. The SES representation with full shading and added contours stands in focus while on the other side a sphere representation of a cluster of atoms with constant shading and without contours provide the context. Thirdly, we propose a hierarchical abstraction based on a set of clusters formed on molecular atoms. All three abstraction models are driven by one importance function classifying the scene into the near‐, mid‐ and far‐field. Moreover, we introduce a methodology to render the entire molecule directly using the A‐buffer technique, which further improves the performance. The rendering performance is evaluated on series of molecules of varying atom counts.     

Optimal Sensor Networks for Area Monitoring Using Rotating and Beam Sensors

We consider the problem of monitoring the Euclidean plane using rotating sensors with detection sectors and beam sensors. We assume that intruders can appear anywhere at any time and move arbitrarily fast, and may have full knowledge of the sensor network. We require that such intruders be detected within a finite amount of time. We give an optimal network for this problem consisting of a combination of rotating sensors of angle 0 and beam sensors that uses the minimum number of both types of sensors. We show a trade-off between the density of beam sensors needed and the angle of the detection sector of the rotating sensors. Secondly, we give a family of sensor networks using only rotating sensors for the same problem, that demonstrate a trade-off between the detection time and the density of rotating sensors used. We show that the density of rotating sensors required in this case can be significantly reduced by increasing the angle of detection sectors. Finally, we show that our results on the infinite plane can be used to derive sensor networks that monitor some finite regions using a density of sensors that is asymptotically the same, or close to that of the infinite plane case.     

Drying-induced stresses in elastic and viscoelastic saturated materials

The paper presents a theoretical analysis of stresses generated during convective drying of kaolin, based on elastic and viscoelastic models. The equations of these models were solved analytically for a cylindrically shaped sample; the distribution and evolution of the radial and circumferential stresses are illustrated in diagrams. The acoustic emission method was used in experimental tests for identification on line of the time period during which the stresses reach their maximal values. A better correlation has been found between the experimental tests and the theoretical predictions obtained on the basis of the viscoelastic model.     

Structure of the cokes obtained from the group components separated from coking coal vitrites by selective thermosolvolysis

The examination of the structure of cokes obtained from extracts separated from preheated vitrites of coking coals by progressive and continuous extraction with chloroform was carried out. The structural ordering (interplanar spacing and crystallite dimensions) of the cokes depends on the rank of the parent vitrites but it does not depend on the degree of extraction. The occurrence of optical anisotropy in cokes from the extracts is connected with both the rank of the parent vitrite and the degree of extraction. In the formation of the optical anisotropic structure during the carbonization of coking coal vitrites, the part of the extract which is of small size, which partially undergoes decomposition, is an important factor.     

Formulations for an inventory routing problem

In this paper, we present and compare formulations for the inventory routing problem (IRP) where the demand of customers has to be served, over a discrete time horizon, by capacitated vehicles starting and ending their routes at a depot. The objective of the IRP is the minimization of the sum of inventory and transportation costs. The formulations include known and new mathematical programming formulations. Valid inequalities are also presented. The formulations are tested on a large set of benchmark instances. One of the most significant conclusions is that the formulations that use vehicle‐indexed variables are superior to the more compact, aggregate formulations.     

Fluidized Bed Air Drying: Experimental Study and Model Development

The presented study describes the processes and mechanisms of batch fluidized bed drying. The influencing factors of hot air drying are theoretically and experimentally examined, in order to present the relations between temperature and humidity profiles and all other drying parameters. A physical model is presented to facilitate the calculation of the drying processes under defined conditions. Three succeeding drying stages are therefore modeled. Mass and energy balances including all components taking part in the process are formulated. The model clarities the drying process under the assumption of pure heat transfer mechanisms. It does not contain adaptive parameters and takes into account an inactive bypass fraction of the fluidization and drying medium. The evaluation of the model was successful for two fluidized bed plants with nominal widths of 100 mm and 400 mm. The experiments showed sufficient accuracy and transferability of the model to equipment of application‐oriented dimensions.