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  • 1
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Heteroatom Chemistry 7 (1996), S. 233-237 
    ISSN: 1042-7163
    Keywords: Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mechanism of the fluxional process occurring in dimeric tetraorganodicarboxylato stannoxanes is presented on the basis of multinuclear NMR studies carried out in noncoordinating solvents. This fluxional process is a consequence of rapid migration of carboxylate groups from one tin atom to the other. It has been proposed that larger carboxylates will also execute this behavior. The effect of cis and trans positions on the fluxional process is discussed. The fluxional process is very fast and could not be stopped even at low temperatures, as measured on the NMR time scale. © 1996 John Wiley & Sons, Inc.
    Additional Material: 4 Ill.
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  • 2
    ISSN: 1042-7163
    Keywords: Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Organotin compounds with the general formula R2(X)SnL (where R=Me, Et, n-Bu, Ph; L=the trans-3-(2-furanyl)-2-propenoate anion or the trans-3-(3-methylphenyl)-2-propenoate anion; and X=Cl) have been prepared by redistribution reactions between the R2SnL2 and R2SnX2 compounds. These compounds were characterized by elemental analyses and various spectroscopic techniques such as 1H, 13C, 119Sn NMR, Mass, Mössbauer, and IR spectroscopies. On the basis of these spectroscopic data, it is suggested that these compounds adopt the cis-R2(X)SnO2 geometry. © 1997 John Wiley & Sons, Inc. Heteroatom Chem 8: 273-278, 1997.
    Additional Material: 6 Tab.
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  • 3
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 39 (1993), S. 369-386 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Nonlinear transport processes in disordered systems such as porous media and heterogeneous solids are studied, which are represented by two- or three-dimensional networks of interconnected bonds, by a Bethe network (a branching network with no closed loops) of a given coordination number, or by a continuum in which circular or spherical inclusions have been inserted at random. The bonds represent the pores of the pore space, or the conducting and insulating regions of a disordered solid, to which we assign effective properties (radii or conductances) selected at random from a probability density function. Three types of nonlinear transport processes are considered. (1) The relation between the current q and the potential gradient v is of power-law type (as in, for example, flow of power-law fluids or the electric current in doped polycrystalline semiconductors). (2) The relation between q and v is piecewise linear, characterized by a threshold (as in flow of Bingham fluids or in mechanical or dielectric breakdown of composite solids). (3) A large v is imposed on the system, so that a linear transport theory is not valid. The behavioral study of the effective transport and topological properties of the system, such as the permeability, conductivity, diffusivity, and the shape of the samplespanning cluster of conducting paths shows that in all cases the concepts of percolation theory play a prominent role, even if the system is well connected and percolation may seem not to play any role. For most cases, new effective-medium approximations (EMAs) are derived for estimating effective transport properties. Compared to the case of linear transport, new EMAs are considerably more accurate in predicting the scaling properties of the transport coefficients near a critical point such as the percolation threshold. For a power-law transport process, an exact solution is also derived for the Bethe networks. Using the concepts of percolation theory, scaling laws relating the effective properties to various regimes of transport and to topological properties of the system are also given. A relation between the volumetric flow rate of a power-law fluid in porous media and the macroscopic pressure drop is derived, which contains no adjustable parameter and is valid at any porosity. To test the accuracy of our analytical predictions, Monte Carlo simulations are carried out for several cases. In most cases, good agreement is found between the simulation results and predictions. The extension of the results to other types of nonlinearities is also discussed.
    Additional Material: 11 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 456-468 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The thermodynamics and transport properties of Lennard-Jones particles in pillared catalytic clays are studied by molecular dynamics simulation. The clays are represented by parallel sheets separated by a given distance and connected by pillars of a given size. Two different spatial distributions of the pillars are studied to determine their effect on the properties of the system. Calculations did not indicate a strong dependence of the diffusivity on the spatial distribution of the pillars, except at low porosities. The solvation force increases monotonically with decreasing porosity of the clays and increasing density of the molecules. The percolation threshold ϕc of the system is estimated from the diffusivity measurements in the limit of infinitely low sorbate densities. Near ϕc the diffusivity D vanishes according to the power law, D ˜ (ϕ - ϕc)n, where ϕ is the porosity of the system, and n is a universal constant. The simulations yield n ⋍ 1.7. Since 2- percolation systems require n ⋍ 1.3 and 3-D systems n ⋍ 2.0, pillared clays behave as a system with an effective dimensionality between 2 and 3.
    Additional Material: 24 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 42 (1996), S. 10-22 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Formation of asphalt aggregates and their deposition on the pore surfaces of a porous medium, which alter the structure of the medium and its effective properties, is a critical problem to catalytic and oil recovery and refinery processes. Extensive new experimental data for the amount of precipitated asphalt formed with crude oil and various solvents are presented. Results indicate that, contrary to the previous assumptions, asphalt formation is at best partially reversible. A thermodynamic model based on the Flory-Huggins theory of polymer solutions is used, together with the Soave equation of state, to predict the data. Critical evaluation of the model shows that its predictions do not agree well with our data. As an alternative, we propose a new model that employs a scaling equation, somewhat similar to those encountered in aggregation and gelation phenomena. The scaling function takes on a very simple form, and its predictions are in very good agreement with the data. It also predicts that the onset of precipitation may obey a simple universal equation.
    Additional Material: 20 Ill.
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  • 6
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 2 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 229-240 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Three different flow and transport phenomena considered here are hydrodynamic dispersion in heterogeneous porous media and aquifers, transport of passive particles in an oscillating flow field, and miscible displacement processes in heterogeneous reservoirs. At microscales all three phenomena are described by the classical convective-diffusion equation (CDE). The presence of long-range correlations at macroscales gives rise to a rich variety of phenomena that cannot be predicted by analyzing the CDE by classical methods. In particular, a new percolation model with long-range correlations provides a rational explanation for the hitherto unexplained field-scale experimental data for hydrodynamic dispersion in porous media and aquifers. Moreover, for transport in oscillating flow in convection cells percolation provides a novel relation between the dispersion coefficient and the Péclet number that cannot be predicted by other methods.
    Additional Material: 9 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 20 (1997), S. 162-170 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The performance of an upflow packed-bed biofilm reactor has been analyzed under multisubstrate limitation by considering simultaneous carbon oxidation and nitrification reactions. The fasting shock load of inlet methanol concentration has a much more pronounced effect on the response of the system compared to that of inlet NH4+ -nitrogen concentration. The exit concentration of NH4+ -nitrogen drops very close to zero, thereby showing essentially complete nitrification during methanol fasting condition. Further, the concentration profiles of oxygen within the biofilm show significant variation during methanol fasting and nonfasting conditions whereas during NH4+ -nitrogen fasting conditions the oxygen concentration profile in the biofilm remains essentially unaffected.
    Additional Material: 6 Ill.
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  • 9
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The performance of a packed-bed biological reactor has been analysed under sinusoidal variations of substrate concentration and temperature for zero-order, first-order and Michaelis-Menten kinetics. The model equations were solved by the method of orthogonal collocation. The results show that the cyclic steady-state conversion is not affected by cyclic variations in the feed concentration. However, cyclic temperature variations with an amplitude of 20°C significantly decrease the mean exit concentration for zero-order and Michaelis-Menten kinetics compared to the constant-temperature case. The approach to cyclic steady-state conditions is estimated to be somewhat flower for zero-order kinetics than for the other kinetics models investigated. We conclude that temperature variations during the day or changes in the performance of upstream plant will not adversely affect the performance of a packed-bed biological reactor.
    Additional Material: 14 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 16 (1993), S. 243-251 
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Using the micromixing concepts of Danckwerts and Zwietering, the Peclet number Pe has been correlated mathematically to the degree of segregation J for the axial dispersion model. The results were applied to compare the micromixing effects on a model, mixed-order parallel reaction system in continuous flow reactors. Axial dispersion model, and Ng and Rippin's two-environment model were used to find the micromixing effects in tubular and stirred tank reactors, respectively. The performance of these reactors, with varying geometries, has been evaluated in terms of overall conversion, selectivity, and yield under identical operating and reaction conditions. The overall conversion increases in a tubular reactor with the increase in J, irrespective of the kinetic orders. However, in a stirred tank reactor, the conversion is found to be micromixing-sensitive, depending on the order of reaction. For m = 1 and n = 2 (case 1), the conversion is fairly insensitive to micromixing effects while it decreases for m = 0.5 and n = 1 (case 2) with increasing J. For the same extent of micromixing, a tubular reactor gives, in both cases, a higher conversion than a stirred tank reactor. The selectivity, in either case, decreases in both reactors with increasing segregation effects. However, in each case, the selectivity of a tubular reactor was fairly close to that of a stirred tank reactor at the same value of J. As far as the yield is concerned, both reactors achieve nearly the same value, without significant micromixing effects.
    Additional Material: 4 Ill.
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