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  • Chemical Engineering
  • 1995-1999  (131)
  • 1
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 151-156 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Thermal diffusivity of high density polyethylene (HDPE) was studied over a wide range of temperatures (25 to 200°C) by melting powdered HDPE in a cylindrical mold at several pressures (101.3 to 5065 KPa gage) and recording the temperature profiles at several radial positions. The energy equation was solved numerically for cylindrical geometry. The thermal diffusivity of HDPE was fit as a function of temperature, porosity, and pressure.
    Additional Material: 8 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 12-22 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An analytical approach to the problem of steady-state, axisymmetrically disperesed, bubbly flow in pipes based on a zero equation turbulence model is discussed. The formulation incorporates recent experimental observations and introduces the effect of bubble size in a rudimentary way. The two-phase mixture is modeled as a variabledensity single fluid assuming an empirical void distribution family. The turbulent shear stress is formed from the contributions of both the velocity and density variation, and the solution of the resulting Reynolds-type equation yields the velocity profile of the flow. Predicted void fraction and velocity distributions agree well with experimental measurements. The main objective of the model is to predict the friction multiplier with minimal computational effort. The velocity profiles of this model agree reasonably well with experiments. Predictions for the friction multiplier are compared to six known and widely used correlations, as well as to experimental data. All the correlations severely underpredict the friction multiplier in the disperesed bubbly flow regime, while the results of our model agree well with the measurements, within the range of its validity.
    Additional Material: 3 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 1874-1888 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A detailed chemical kinetics model comprising 148 reversible elementory reactions for the supercritical water oxidation (SCWO) of methane, methanol, carbon monoxide and hydrogen was developed. Rate constants were taken from previous critical evaluations. The Lindemann model, at times modified with a broadening parameter, was used to account for the effects of pressure on the kinetics of unimolecular reactions. Model predictions were compared with published experimental SCWO kinetics data for 450-650°C and 240-250 atm. The model correctly predicted global reaction orders for all four fuels to within their uncertainties. In addition, the model correctly predicted that the global reaction orders for O2 during methanol and hydrogen oxidation were essentially zero, and that the O2 concentration had the greatest effect on the methane oxidation rate. The pseudo-first-order rate constants predicted by the model were consistently higher than the experimental values, but the global activation energies were predicted correctly for methane oxidation and for CO and H2 oxidation at high temperatures. The model's predictions generally became worse as the temperature decreased toward the critical point of water. A sensitivity analysis revealed that fewer than 20 elementaty reactions largely controlled the oxidation kinetics for the compounds studied. Nearly half of these reactions involved HO2, which is an important free radical for SCWO. Quantitative agreement with the experimental methane conversions was obtained by adjusting the preexponential factors for three elementary reactions within their uncertainties. It could also be obtained by using the JANAF value (0.5 kcal/mol) for the standard heat of formation of HO2, but this value is lower than other recently recommended values.
    Additional Material: 11 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 1005-1009 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Partial specific volumes at 25°C are reported for α-chymotrypsinogen in aqueous solutions containing NaCl, citrate, and/or polyethylene gycol (PEG) over a range of protein concentrations. The concentration dependence of the partial specific volume can be either positive or negative, depending on the solvent. For example, the partial specific volume increases with increasing protein concentration in NaCl/citrate solutions at high salt concentrations, and decreases with increasing protein concentration in solutions containing PEG. Kirkwood-Buff solution theory has been applied to interpret these results, and it was found that the concentration dependence is determined by two factors: (1) the effective or solvent-averaged interactions between protein molecules in solution, and (2) three-body protein - protein - solvent and protein - solvent - solvent interactions. An approach is proposed for the experimental determination of both contributions that involves measuring osmotic pressures and volumetric properties of dilute to concentrated protein solutions.
    Additional Material: 1 Tab.
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  • 5
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 42 (1996), S. 3055-3062 
    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 inverse probability theorem of Bayes is used, along with sampling theory, to obtain objective criteria for choosing among rival models. Formulas are given for the relative posterior probabilities of candidate models and for their goodness of fit, when the models are fitted to a common data set with Normally distributed errors. Cases of full, partial and minimal variance information are treated. The formulas are demonstrated with three examples, including a kinetic study of a catalytic reaction.
    Additional Material: 5 Tab.
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  • 6
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 1723-1778 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Supercritical fluids posses properties that make them attractive as media for chemical reactions. Conducting chemical reactions at supercritical conditions affords opportunities to manipulate the reaction environment (solvent properties) by manipulating pressure, to enhance the solubilities of reactants and products, to eliminate interphase transport limitations on reaction rates, and to integrate reaction and separation unit operations. Supercritical conditions may be advantageous for reactions involved in fuels processing, biomass conversion, biocatalysis, homogeneous and heterogeneous catalysis, environmental control, polymerization, materials synthesis, and chemical synthesis. Moreover, supercritical fluids can be used profitably in fundamental chemical investigations of intermolecular interactions and their influence on chemical processes. Work on chemical reactions in and with supercritical fluids is reviewed. We discuss both fundamental studies and applications of reactions at supercritical conditions, with focus on work published after 1985.
    Additional Material: 43 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 83-90 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Large, high-quality, single crystals of pure-silica ferrierite are synthesized, and the structure is described. Selected individual crystals (approximately 600 μm X 500 μm X 20 μm) are mounted in a membrane configuration so that only the 10-membered-ring channels (5.4 Å X 5.4 Å X 4.2 Å) or the 8-membered-ring channels (4.6 Å X 3.7 Å X 3.0 Å) are accessible for gas-molecule permeation. The first examples of transport exclusively through 8- or 10-membered-ring channel systems are reported and obtained through crystal orientation in the membrane. A series. of adsorption experiments are conducted to help select suitable probe molecules and evaluate the role of adsorption in the permeation process for single-crystal membranes. Methane, n-butane, isobutane and nitrogen probe molecules are used to study intracrystalline sorption and transport effects for different crystal orientations, pressures and temperatures. Both pure-gas selectivities and mixed-gas separation factors are reported. A mixed-gas separation factor of n-butane/isobutane = 116 for the 10-membered-ring orientation of the crystal at 383 K and a transmembrane pressure difference of 1.01 X 105 Pa are found using this technique. In addition, molecular sieving is observed for the 8-membered-ring orientation of the crystal since methane, but not butane, transport is observed for this crystal orientation.
    Additional Material: 6 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Process Safety Progress 17 (1998), S. 219-224 
    ISSN: 1066-8527
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Sandia National Laboratories (Sandia) has refined a process for developing inherently safer system designs based on methods used by Sandia to design detonation safety into nuclear weapons. The process was created when Sandia realized that standard engineering practices did not provide the level of safety assurance necessary for nuclear weapon operations, with their potential for catastrophic accidents. A systematic approach, which relies on mutually supportive design principles integrated through fundamental physical principles, was developed to ensure a predictably safe system response under a variety of operational and accident-based stesses. Robust, safe system designs result from this thematic approach to safety, minimizing the number of safety critical features. This safety assurance process has two profound benefits: the process avoids the need to understand or limit the ultimate intensity of off-normal environments and it avoids the requirement to analyze and test a large array of accident environment scenarios (e.g., directional threats, sequencing of environments, time races, etc) to demonstrate conformance to all safety requirements.
    Additional Material: 3 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 35 (1995), S. 1282-1289 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The creep behavior of polymers depends on the physical age of the material at the time of stress application. Creep curves shift to longer times for more highly aged material and, in poly(vinyl chloride), (PVC), this can be modeled by an empirical equation in which the magnitude of an effective mean retardation time parameter is dependent upon, and increases with, the age of the polymer. Creep compliances for PVC also depend on the magnitude of the applied stress when this exceeds about 4 MPa. This nonlinear behavior is caused, at short creep times, by a reduction in the value for the retardation time parameter on application of the creep stress. Specimens appear therefore to be initially de-aged by elevated stresses. Subsequently, this parameter increases with creep time implying that physical aging has been reactivated, but the rate of increase also depends on the stress level. These influences of elevated stresses can be described by an extension of the creep model, and parametric expressions have been derived which relate creep compliance values to time, stress, and the age of the polymer. It is shown how the parameters can be determined from a short series of creep experiments and thus how creep deformations can be calculated over wide ranges of time, stress, and age.
    Additional Material: 10 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    Brookfield, Conn. : Wiley-Blackwell
    Polymer Composites 16 (1995), S. 319-324 
    ISSN: 0272-8397
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: This paper deals with the conductivity of binary polymer composites filled with an electronically conductive material. A “dynamic cluster model” is offered to describe the conductivity of such polymer composites in the highly filled region, i.e. above the percolation threshold. The model is based on the following assumptions: 1a modification of the basic statistical percolation equation, i.e. σ (ϕ-ϕc)t, where t = 1.6 to 1.9, should be applied for all systems in the highly filled region, although application is limited to the range ϕ = ϕc + Δϕ, Δϕ ⇒ 0 in the strict statistical percolation approach;2the most important modifications with respect to the basic equation of the statistical percolation theory are (a) the use of a constant teff, including a constant part t1 (resembling “t” in the basic statistical percolation approach) and a variable part t2 (depending on the filler concentration ϕ of the specific mixture) and(b) the definition of ϕc as the filler concentration where a perfect three-dimensional network of the conductive phase has been established. This idea has been adopted from the bond-percolation approach of Aharoni;3the resulting equation should include parameters of specific polymer composites.The generalized equation σ = f(ϕ) is used to calculate the maximum possible conductivity of a certain mixture as well as the dependence of σ on the filler content.
    Additional Material: 6 Ill.
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