Periodic Fluctuations of Flow and Porosity in Spouted Beds

The results of experimental investigations of bed flow hydrodynamics in spouted beds are compared with CFD simulations (Eulerian–Eulerian approach) for two different column geometries. The experimental results of bed porosity and fluctuation frequency of mass flow rate of grain in the fountain region are compared with the corresponding results of simulations. The simulation results confirmed the observations of Muir et al. (1990, Chem. Eng. Comm. 88: 153–171) and Yang and Keairns (1978, AlchE Symp. Ser. No. 176 74: 218) that fluctuations of bed flow in DTSB are caused by particle cluster formation in the loading region at the bottom of column. The solids cross into the jet and cover the column inlet and are carried upward periodically through a draft tube. Subsequent figures obtained from simulations, which show stages of particle cluster formation at the entrance of column, exactly match visual observations. The frequency of fluctuations of grain mass flow rate predicted in simulations (~5–6 Hz) is in the range of that experimentally determined. The fluctuating inflow of solids results in slug formation and explains the vertical variations of height and porosity of the fountain.     

Drying Induced Stresses in a Swelling Porous Wall

The present paper is concerned with the stresses generated in a capillary-porous wall saturated from the bottom and dried naturally on its side planes. The upper cross-section of the wall is totally isolated and no heat and moisture transfer occurs through it, while the bottom one has an a priori determined temperature and moisture content. The vertical planes of the wall are surrounded by air having different temperatures and moisture contents on the left and the right sides. The problem is solved numerically based on a mechanistic model of drying earlier developed by the authors. The distributions of temperature, moisture content, and the drying induced stresses are determined. The variation of temperature on the wall left and right surfaces is analysed dependent on the surroundings temperature. The influence of boundary conditions on the stress distribution in the wall is discussed.     

Elastic arches with large elevation. Singularly perturbed problem of nonlinear elasticity

In this paper we examine the asymptotic expansion of a three-dimensional displacement field defined over a slender, bowlike domain whose shape corresponds to a thin arch. We show that it is possible to derive from the principles of virtual work two families of arch equations whose forms vary with the scale of external forces and the curvature of the arch. The first family of models, for relatively small curvatures, is described by singularly perturbed ordinary differential equations. The second family, when the curvature of the original arch is large, is described by two-dimensional partial differential equations whose form depends on the shape of the cross-section of the solid arch.     

Effective eddy viscosities in implicit modeling of decaying high Reynolds number turbulence with and without rotation

We assess the applicability of the numerical dissipation as an implicit turbulence model. The nonoscillatory finite volume numerical scheme MPDATA developed for simulations of geophysical flows is employed as an example of a scheme with an implicit turbulence model. A series of low resolution simulations of decaying homogeneous turbulence with and without Coriolis forces in the limit of zero molecular viscosity are performed. To assess the implicit model the long-time evolution of turbulence in the simulations is investigated and the numerical velocity fields are analyzed to determine the effective spectral eddy viscosity that is attributed to the numerical discretization. The detailed qualitative and quantitative comparisons are made between the numerical eddy viscosity and the theoretical results as well as the intrinsic eddy viscosity computed exactly from the velocity fields by introducing an artificial wave number cutoff. We find that the numerical dissipation depends on the time step and exhibits contradictory dependence on rotation: it is overestimated for rapid rotation cases and is underestimated for nonrotating cases. These results indicate that the numerical dissipation may fail to represent the effects of the physical subgrid scale processes unless the parameters of a numerical scheme are carefully chosen.     

A Criterion for Compatibility of Conformal and Projective Structures

In a space-time M, a conformal structure is defined by the distribution of light-cones. Geodesics are traced by freely falling particles, and the collection of all unparameterized geodesics determines the projective structure of M. The article contains a formulation of the necessary and sufficient conditions for these structures to be compatible, i.e. to come from a metric tensor which is then unique up to a constant factor. The theorem applies to all dimensions and signatures.     

Adaptive linear combination of heuristic orderings in constructing examination timetables

In this paper, we investigate adaptive linear combinations of graph coloring heuristics with a heuristic modifier to address the examination timetabling problem. We invoke a normalisation strategy for each parameter in order to generalise the specific problem data. Two graph coloring heuristics were used in this study (largest degree and saturation degree). A score for the difficulty of assigning each examination was obtained from an adaptive linear combination of these two heuristics and examinations in the list were ordered based on this value. The examinations with the score value representing the higher difficulty were chosen for scheduling based on two strategies. We tested for single and multiple heuristics with and without a heuristic modifier with different combinations of weight values for each parameter on the Toronto and ITC2007 benchmark data sets. We observed that the combination of multiple heuristics with a heuristic modifier offers an effective way to obtain good solution quality. Experimental results demonstrate that our approach delivers promising results. We conclude that this adaptive linear combination of heuristics is a highly effective method and simple to implement.     

The t-Tone Chromatic Number of Random Graphs

A proper 2-tone k-coloring of a graph is a labeling of the vertices with elements from \({\binom{[k]}{2}}\) such that adjacent vertices receive disjoint labels and vertices distance 2 apart receive distinct labels. The 2-tone chromatic number of a graph G, denoted τ ₂(G) is the smallest k such that G admits a proper 2-tone k coloring. In this paper, we prove that w.h.p. for \({p\geq Cn^{-1/4} {\rm ln}^{9/4}n, \tau_2(G_{n, p}) = (2 + o(1))\chi(G_{n, p})}\) where \({\chi}\) represents the ordinary chromatic number. For sparse random graphs with p = c/n, c constant, we prove that \({\tau_2(G_{n, p}) = \lceil{({\sqrt{8\Delta + 1} + 5})/{2}}}\) where Δ represents the maximum degree. For the more general concept of t-tone coloring, we achieve similar results.     

Robust Markov perfect equilibria

In this paper we study a Markov decision model with quasi-hyperbolic discounting and transition probability function depending on an unknown parameter. Assuming that the set of parameters is finite, the sets of states and actions are Borel and the transition probabilities satisfy some additivity conditions and are atomless, we prove the existence of a non-randomised robust Markov perfect equilibrium.     

Reactivity of chemisorbed oxygen atoms and their catalytic consequences during CH4-O2 catalysis on supported Pt clusters

Kinetic and isotopic data and density functional theory treatments provide evidence for the elementary steps and the active site requirements involved in the four distinct kinetic regimes observed during CH(4) oxidation reactions using O(2), H(2)O, or CO(2) as oxidants on Pt clusters. These four regimes exhibit distinct rate equations because of the involvement of different kinetically relevant steps, predominant adsorbed species, and rate and equilibrium constants for different elementary steps. Transitions among regimes occur as chemisorbed oxygen (O*) coverages change on Pt clusters. O* coverages are given, in turn, by a virtual O(2) pressure, which represents the pressure that would give the prevalent steady-state O* coverages if their adsorption-desorption equilibrium was maintained. The virtual O(2) pressure acts as a surrogate for oxygen chemical potentials at catalytic surfaces and reflects the kinetic coupling between C-H and O═O activation steps. O* coverages and virtual pressures depend on O(2) pressure when O(2) activation is equilibrated and on O(2)/CH(4) ratios when this step becomes irreversible as a result of fast scavenging of O* by CH(4)-derived intermediates. In three of these kinetic regimes, C-H bond activation is the sole kinetically relevant step, but occurs on different active sites, which evolve from oxygen-oxygen (O*-O*), to oxygen-oxygen vacancy (O*-*), and to vacancy-vacancy (*-*) site pairs as O* coverages decrease. On O*-saturated cluster surfaces, O*-O* site pairs activate C-H bonds in CH(4) via homolytic hydrogen abstraction steps that form CH(3) groups with significant radical character and weak interactions with the surface at the transition state. In this regime, rates depend linearly on CH(4) pressure but are independent of O(2) pressure. The observed normal CH(4)/CD(4) kinetic isotope effects are consistent with the kinetic-relevance of C-H bond activation; identical (16)O(2)-(18)O(2) isotopic exchange rates in the presence or absence of CH(4) show that O(2) activation steps are quasi-equilibrated during catalysis. Measured and DFT-derived C-H bond activation barriers are large, because of the weak stabilization of the CH(3) fragments at transition states, but are compensated by the high entropy of these radical-like species. Turnover rates in this regime decrease with increasing Pt dispersion, because low-coordination exposed Pt atoms on small clusters bind O* more strongly than those that reside at low-index facets on large clusters, thus making O* less effective in H-abstraction. As vacancies (*, also exposed Pt atoms) become available on O*-covered surfaces, O*-* site pairs activate C-H bonds via concerted oxidative addition and H-abstraction in transition states effectively stabilized by CH(3) interactions with the vacancies, which lead to much higher turnover rates than on O*-O* pairs. In this regime, O(2) activation becomes irreversible, because fast C-H bond activation steps scavenge O* as it forms. Thus, O* coverages are set by the prevalent O(2)/CH(4) ratios instead of the O(2) pressures. CH(4)/CD(4) kinetic isotope effects are much larger for turnovers mediated by O*-* than by O*-O* site pairs, because C-H (and C-D) activation steps are required to form the * sites involved in C-H bond activation. Turnover rates for CH(4)-O(2) reactions mediated by O*-* pairs decrease with increasing Pt dispersion, as in the case of O*-O* active structures, because stronger O* binding on small clusters leads not only to less reactive O* atoms, but also to lower vacancy concentrations at cluster surfaces. As O(2)/CH(4) ratios and O* coverages become smaller, O(2) activation on bare Pt clusters becomes the sole kinetically relevant step; turnover rates are proportional to O(2) pressures and independent of CH(4) pressure and no CH(4)/CD(4) kinetic isotope effects are observed. In this regime, turnover rates become nearly independent of Pt dispersion, because the O(2) activation step is essentially barrierless. In the absence of O(2), alternate weaker oxidants, such as H(2)O or CO(2), lead to a final kinetic regime in which C-H bond dissociation on *-* pairs at bare cluster surfaces limit CH(4) conversion rates. Rates become first-order in CH(4) and independent of coreactant and normal CH(4)/CD(4) kinetic isotope effects are observed. In this case, turnover rates increase with increasing dispersion, because low-coordination Pt atoms stabilize the C-H bond activation transition states more effectively via stronger binding to CH(3) and H fragments. These findings and their mechanistic interpretations are consistent with all rate and isotopic data and with theoretical estimates of activation barriers and of cluster size effects on transition states. They serve to demonstrate the essential role of the coverage and reactivity of chemisorbed oxygen in determining the type and effectiveness of surface structures in CH(4) oxidation reactions using O(2), H(2)O, or CO(2) as oxidants, as well as the diversity of rate dependencies, activation energies and entropies, and cluster size effects that prevail in these reactions. These results also show how theory and experiments can unravel complex surface chemistries on realistic catalysts under practical conditions and provide through the resulting mechanistic insights specific predictions for the effects of cluster size and surface coordination on turnover rates, the trends and magnitude of which depend sensitively on the nature of the predominant adsorbed intermediates and the kinetically relevant steps.