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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
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 5 (1991), S. 291-298 
    ISSN: 0886-9383
    Keywords: Absorbance ratio ; Statistical confidence ; Quality control ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ratio measurements are commonly used to address a variety of analytical problems in environmental, forensic and pharmaceutical laboratories. In absorbance ratioing techniques, analytical chemists rely on the spectral features of the analyte(s) of interest. The absorbances at two wavelengths are monitored and the ratio of these two absorbances is computed. This ratio is then used to confirm the identity of the analyte(s) of interest, the purity of a product of the overlap of chromatographic peaks. These decisions often have far-reaching consequences (e.g. the identification of the source, biogenic or petrogenic, of hydrocarbons in biological tissues or water). Given the cost and the liabilities associated with such decisions, it is unfortunate that these ratios are seldom reported with any statistical confidence. The purpose of this study is to delineate the parameters that affect absorbance ratio measurements. The models that can be used to estimate the statistical confidence in these measurements are derived and evaluated experimentally. The results show that these models can estimate the relative standard deviations in absorbance ratios accurately. They can also estimate the effect of signal-to-noise ratio and the choice of wavelengths on the precision of absorbance ratios.
    Additional Material: 2 Ill.
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  • 4
    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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  • 5
    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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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Chemical Engineering & Technology - CET 20 (1997), S. 10-16 
    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 dual substrate limitation conditions. The numerical solution of the proposed equations defining the system has been obtained for a wide range of operating conditions for a case of practical significance involving glucose and oxygen as dual substrates. The results show that the inlet glucose concentration defines the limiting substrate at a position near the inlet of the reactor. For inlet glucose concentrations up to 300 mg/l, glucose acts as the limiting substrate. However, for inlet concentrations of 400 mg/l of glucose or higher, oxygen assumes the role of the limiting substrate at that position. For all other positions in the reactor, glucose acts as the limiting substrate, irrespective of its inlet concentration. Extensive computations were performed in order to define regions where glucose, oxygen or both are limiting. The predicted results have been found to be in agreement with the theoretical criteria, proposed in the literature, of determining the limiting substrate.
    Additional Material: 8 Ill.
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  • 7
    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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  • 8
    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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  • 9
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 42 (1996), S. 3318-3332 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Extensive small-angle X-ray and neutron-scattering data, as well as results of precipitation measurements, are analyzed to delineate the structure of the asphalt and asphaltene aggregates that are formed when a solvent is injected into a system containing crude oil. The two types of data strongly suggest that both small and large aggregates have a fractal structure, with well-defined fractal dimensions. If the system is aged long enough at low enough temperature, large asphalt particles will have the structure of diffusion-limited cluster-cluster aggregates with a fractal dimension Df ≃ 1.8, while the small ones are similar to diffusion-limited particle aggregates with a fractal dimension df ≃ 2.5. High temperatures increase the rotational motion of the particles, disturb the structure and mechanical stability of the aggregates, and decrease their fractal dimension. Aging and concentration effects of the asphalts in the solution, and the type of the solvent on the structure of the aggregates are also investigated. Implications of these results for the structure, mechanical stability, and molecular-weight distribution of asphalts and asphaltenes are detailed. A new molecular-weight distribution for asphalt aggregates predicts the experimental data excellently.
    Additional Material: 16 Ill.
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  • 10
    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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