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  • Engineering General  (1,952)
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  • 1995-1999  (1,123)
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  • 101
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 31 (1991), S. 47-55 
    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: A feasibility study on the use of vibration spectrum analysis as a tool for nondestructive evaluation (NDE) of polymer composites was conducted. Material integrity of polymer composite samples was determined from the vibrational measurements by analyzing the resonant frequency and damping information. A number of important “states” in the composites tested could be characterized by this analysis. The vibration tehnique was found to be sensitive to physical flawing (fiber breakage, delamination, and matrix cracking). Vibrational NDE has many potential advantages that make it very attractive for composite applications. These include the ability to make global measurements of large structures in real-time, no geometry restrictions, and high sensitivity to a wide variety of damage states.
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  • 102
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    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 31 (1991), S. 56-60 
    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: Resin transfer molding (RTM) of advanced fiber architecture materials promises to be a cost effective process for obtaining composite parts with exceptional strength. However there are a larger number of material processing parameters that must be observed, known, and/or controlled during the resin transfer molding process. These include the viscosity both during impregnation and cure. In-situ sensors which can observe these processing properties within the RTM tool during the fabrication process are essential. This paper will discuss recent work on the use of frequency dependent electromagnetic sensing (FDMS) techniques to monitor these properties in the RTM tool. Our objective is to use these sensing techniques to address problems of RTM scaleup for large complex parts and to develop a closed loop, intelligent, sensor controlled RTM fabrication process.
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  • 103
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 37 (1991), S. 111-122 
    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 time-averaged void fraction, pressure drop and flow regime transition behavior of horizontal air-water two-phase flows is studied experimentally and numerically for 2-cm-inner-diameter tubes with various flow dividing junctions at its end. The time-average void and pressure drop behavior along the channel is simulated using a two fluid separated flow model. The results show that two-phase behavior (flow regime, void fraction, and pressure drop) is affected strongly by the presence of a flow division in the system. These effects extend far upstream of the junction for low-momentum flows and far downstream for high-momentum flows. Both numerical and experimental results show that there occurs a large increase in void just downstream of the junction owing to the halving of the fluid volume flow rates and the liquid deceleration.
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  • 104
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 37 (1991), S. 137-141 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 105
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 37 (1991) 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 106
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 37 (1991), S. 169-181 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Nonequilibrium diffusion behavior in nonionic and ionic surfactant microemulsion systems has been studied experimentally using the open-ended capillary method. Experimental results for these systems have been compared with a drop theory of diffusion for microemulsions under conditions where large concentration and electrostatic gradients exist. The results show good agreement in concentration profiles between theory and experiment for the microemulsion components - water, benzene, and phenol. Furthermore, under certain conditions the theory predicts that over a limited time interval phenol will diffuse from low-concentration regions to regions of higher concentration. This phenomenon has been observed.
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  • 107
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 37 (1991), S. 225-232 
    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 parametric sensitivity criteria were examined for application to a pseudohomogeneous tubular reactor system, in which both methanol dehydration (exothermic) and methanol dissociation (endothermic) were catalyzed. The addition of the endothermic reaction was shown to lead to a desensitized reactor. It was illustrated, however, that the relative activities of the two catalysts should be somewhat similar to maintain the overall conversion of the resulting reactor for a given residence time.The three criteria investigated tended to disagree with one another more, as the system was made less sensitive by the addition of more endothermic catalyst. A potential application of the resulting nonsensitive reactor design would be in methanol-fueled vehicles.
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  • 108
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 37 (1991), S. 597-606 
    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 tray hydrodynamics were determined for a system containing water and kerosene as immiscible liquids. Plates with hole diameters ranging from 3.18 to 12.70 mm were used in a 44.5-cm2 perspex air-water-kerosene simulator. Experiments were also carried out in a 50-mm-ID column using different depths of oil and water mixtures to study the drop and bubble mechanisms. A spray-to-bubble transition occurred for the two liquid-phase system experiments. The liquid holdup at the transition increased directly with gas velocity and hole diameter, and decreased with increasing free area. At the same hole velocity, the presence of two liquid phases caused the transition to occur at different liquid holdups than for the single pure liquid. Two different modes of coalescence were observed in the small column work. New correlations have been proposed for the liquid holdup at the transition which allow for the presence of two liquid phases.
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  • 109
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 110
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    AIChE Journal 37 (1991), S. 803-803 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 111
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 37 (1991) 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 112
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    AIChE Journal 37 (1991), S. 1009-1018 
    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 computational study of fully-developed flow of gas-particle suspensions in vertical pipes was carried out, using the model proposed recently by Sinclair and Jackson (1989), to understand the predicted scale-up characteristics. It was shown that the model can capture the existence of steady-state multiplicity wherein different pressure gradients can be obtained for the same gas and solids fluxes. A pronounced and nonmonotonic variation of the pressure gradient required to achieve desired fluxes of solid and gas with tube diameter was predicted by the model, and this is explained on a physical basis. The computed results were compared with the experimental data. The model manifests an unsatisfactory degree of sensitivity to the inelasticity of the particle-particle collisions and the damping of particle-phase fluctuating motion by the gas.
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  • 113
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    AIChE Journal 37 (1991), S. 1109-1112 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 114
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 37 (1991), S. 1121-1128 
    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 solubility of L-serine in water was measured as a function of temperature, and the solubility in methanol-water solutions was determined as a function of temperature and methanol concentration. Solubility in aqueous solutions was found to be a linear function of temperature. Additionally, a statistical design of experiments was used to identify the kinetic variables that influence the purity of L-serine crystals recovered by batch crystallization. Agitation and the rate at which super-saturation was generated through cooling and methanol addition were found to influence the methanol content of the recovered crystals. The size of the recovered crystals also was found to depend on agitation and the rate at which methanol was added to the L-serine mother liquor.
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  • 115
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    AIChE Journal 37 (1991), S. 1139-1150 
    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 emulsion layer model is presented which predicts the thickness of a downward-moving emulsion layer along the wall of a circulating fluidized bed, the mean solids velocity, and the solids flux in the layer. Also presented is a heat transfer model which, in combination with the emulsion layer model, predicts the low-temperature data very well. An alternate slab model proposed for the radiative component in a high-temperature circulating fluidized bed agrees well with experimental data. The heat transfer predictions of the overall model for such operating parameters as solid circulation flux, suspension temperature, length of the heat transfer surface, superficial gas velocity, and mean particle size are in good agreement with the published data for long surfaces.
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  • 116
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    AIChE Journal 37 (1991), S. 1187-1195 
    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 sorption behavior of water and ethanol on starch material has been investigated in relation to the adsorptive separation of water from ethanol. The adsorption isotherms of water-starch, ethanol-starch and water-ethanol-starch were measured using a Cahn electrobalance. Careful examination of the many sorption isotherm models resulted in selection of Sircar's model and the potential theory to best represent the isotherm data of water-starch and ethanol-starch adsorption. Experimental results showed that ethanol as well as water can adsorb on starch. The adsorption rate of ethanol, however, is much slower than that of water. This suggests that the selective removal of water from ethanol vapor in a packed-bed adsorber is likely a rate-dependent, not an equilibrium-dependent, process.
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  • 117
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 37 (1991), S. 1196-1204 
    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 influence of various operating and liquid-phase physical variables on interfacial area ab in cylindrical and spherical gas-liquid stirred contactors was studied using the sulfite method. Studied were stirring speed, sparger porosity, gas flow rate, liquid-phase temperature, surface tension, and pH.The results show that the influence of operating variables (gas flow rate Qg, stirring speed ω, and the average pore radius of the sparger used rp) on ab, for both types of contactors, can be given by the equation: \documentclass{article}\pagestyle{empty}\begin{document}$$ a_b = Q_g^{0.5} \left({\frac{{k_1 }}{{k_2 }} + \frac{{k_2 }}{{r_p^{1.5} }}\omega } \right) $$\end{document} Dependency of ab on surface tension observed was believed to be caused by a rising rate of bubble coalescence with increased surfactant concentration. The higher the surfactant concentration, the lower ab, tending to a limit that depends on both the type of surfactant and the average size of sparger pore used. Due to the measurement method used, solution pH and temperature were also observed to influence ab.
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  • 118
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    AIChE Journal 37 (1991), S. 1219-1226 
    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 correlation was developed to quantitatively describe the flux in a high-speed rotating filtration device using a minimum set of parameters. The experimental results were found to be consistent with the concentration polarization (CP) model. Beyond a threshold pressure flux ceases to depend on membrane permeability. The CP model was modified to include the concentration dependence of the diffusivity. This approach was found to be consistent with the strong dependence of flux on pH. Protein concentration in the polarized layer adjacent to the membrane surface was estimated using a procedure that corrects for some of the inconsistencies in the methods usually applied. Four dimensionless numbers were necessary to correlate the experiments with good accuracy. Previously-reported correlations used only three dimensionless numbers. Usage of four numbers could be justified by dimensional analysis. Finally, the performance of rotary or vortex filtration was compared to that of other configurations.
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  • 119
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    AIChE Journal 37 (1991), S. 1255-1260 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 120
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    AIChE Journal 37 (1991), S. 1249-1254 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 121
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    AIChE Journal 37 (1991), S. 1270-1274 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 122
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    AIChE Journal 37 (1991), S. 1305-1317 
    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 problem of freely-suspended liquid droplets deforming due to an applied electrostatic field is examined. Developed is a numerical model capable of predicting the complete transient histories of droplets in systems with a wide range of dispersedand continuous-phase densities, viscosities, relative permittivities, and electric field strengths. For liquid/gas systems, the predictions of the numerical model demonstrated that the critical field strength and critical permittivity ratio during actual transient breakup are not necessarily the same as those predicted by steady-state theories. An approximate analytical model of transient droplet deformation is also developed, which is able to predict the deformation time histories for large Ohnesorge number, small-deformation liquid/liquid systems. The approximate analytical model agreed well with the results of the complete numerical model.
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  • 123
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    AIChE Journal 37 (1991), S. 1341-1353 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: We present an explicit analytical solution for the Lévêque's problem with the boundary condition of the third kind. This solution is applicable to problems of mass (heat) transfer with surface reaction (surface resistance) in the entry region of fully developed flow fields of power law fluids, and to the developing boundary layer flows that admit Falkner-Skan solutions, provided that the Schmidt (Prandtl) number is large. The series form of the solution developed by inversion of the Laplace transform has excellent convergence properties within the concentration (temperature) boundary layer in contrast to the integral forms that are usually reported for problems of this type. An efficient computational algorithm for evaluation of the surface concentration is presented, as well as accurate approximate formulas in the form of simple algebraic expressions for the local and average mass (heat) transfer coefficients and the surface concentration (temperature).
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  • 124
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    AIChE Journal 37 (1991), S. 1789-1800 
    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 finite element method was used to model microwave thawing of pure-water and 0.1-M NaCl cylinders. The electromagnetic field was described by Maxwell's equations with temperature-dependent dielectric properties, while the heat equation, coupled with the Stefan and Robin conditions, was used to describe the thawing process. An additional equation for the frozen volume fraction was used, when necessary, to account for the presence of a mushy region. Two microwave frequencies, 915 MHz and 2,450 MHz, were examined and the microwave radiation was assumed to be radially isotropic and normal to the surface of the cylinder. Results show that a two-phase mushy region may exist, and an additional thawing front may appear at the center of the cylinder. Salt cylinders have a higher dielectric loss than pure-water cylinders and therefore thaw more quickly. Internal resonance occurs when the wavelength of the radiation is a harmonic of the cylinder radius. Resonance increases power deposition and expedites the thawing process. The onset of resonance alters thawing times and complicates the development of heuristic rules for microwave thawing.
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  • 125
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    AIChE Journal 37 (1991), S. 1833-1843 
    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 experimental study of the dynamics of electrodissolution of iron in sulfuric acid is reported. The experiments were done under potentiostatic conditions with a rotating disk electrode as a function of two parameters, potential and electrode diameter. The dynamic behavior depends strongly on the latter parameter; with increasing electrode size we observe transitions from periodic oscillations to low-order chaos to higher-order chaos. The attractor dimension increases with increasing electrode size. In addition, for the large electrodes at more positive potentials, a secondary higher frequency oscillation also arises.
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  • 126
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    AIChE Journal 37 (1991), S. 1863-1874 
    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 generalized technique for modeling resist performance is outlined. In this approach, the fraction of resist remaining after development as a function of incident dose, or characteristic curve, is related to the development rate which is assumed to be a power law of a dominant soluble species. Soluble species are either photochemically consumed for negative resists or generated for positive. Expressions for the dependence of characteristic curves on exposure dose and chemistry are derived for various resist systems, which are consistent with current models. For similar chemical kinetics, negative resists yield fewer lumped parameters to describe their development rate and characteristic curves than positive.Under conditions of negligible surface inhibition, lumped parameters can be extracted from characteristic curves and used to simulate lithography. A generalized method to correct for absorption in the resist and reflections is outlined. Exposure latitude was accurately predicted for a commercial negative chemically amplified resist. However, prediction of linewidths from characteristic curves of positive resists is complicated by surface inhibition effects.
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    AIChE Journal 37 (1991), S. 1905-1906 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 128
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    AIChE Journal 37 (1991), S. 429-436 
    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 sensitivity of the calculated micropore size of zeolite Y in a fluidized cracking catalyst based on empirical models for argon adsorption has been tested by examining the effect of curvature and by systematically verifying the magnitude of physical constants in the model equations. With a consistent set of physical parameters the slit model provided a pore size value of 0.45 nm, while the new cylindrical models provided values of 0.69 and 0.74 nm. The latter values are found to correspond well with the known aperture size of zeolite Y, 0.74 nm. By separately varying the magnitudes of five of the physical constants in the model over a range of ±30%, it was concluded that the diameter of the oxide ion at the surface had a large effect on the calculated pore size, while the other parameters had only moderate to small effects. Preliminary application of the cylindrical pore model to isotherms of argon on other zeolites and molecular sieves leads to promising results, especially for medium to large pore zeolites. These results suggest that the cylindrical pore model is a useful means for the transformation of argon adsorption data on a zeolite into a micropore size distribution.
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    AIChE Journal 37 (1991), S. 461-465 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 37 (1991), S. 448-460 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Efforts to model the turbulent flow in stirred tanks require accurate boundary conditions at the tip of the impeller, not just of velocities, but of the turbulence quantities k and ε. Kolar's (1982) phenomenological, swirling radial jet model of the impeller region is extended by using a two-equation k - ε turbulence model to obtain direct estimates of k and ε on the impeller periphery. The model is extended and clarified, so that the number of parameters required for its application is reduced to two: the rotational speed and the diameter of the impeller. Three-dimensional simulations allow a realistic treatment of the baffles. Agreement of the modeling results with recently published experimental data is excellent. This is particularly true in the important impeller discharge zone, where details of the predicted behavior of the turbulence kinetic energy and dissipation rate are in quantitative agreement with the available data. Based on these results, average values of ε are calculated, along with the zones over which the apply. For the impeller discharge zone, the dimensionless, volume-averaged ε is 0.19.
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    AIChE Journal 37 (1991), S. 475-479 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 37 (1991), S. 499-511 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Simple distillation columns with ideal vapor-liquid equilibrium may display multiple steady-state solutions. Two fundamentally different sources for the multiplicity are presented. Both bring about the unexpected result that increasing reflux makes separation worse in the top part of the column. It corresponds to an unstable operating point.The first type of multiplicity is found for columns with mass or volume inputs (e.g., mass reflux and molar boilup). Even for constant molar flows, the transformation from the actual input units to molar units may become singular (corresponding to a pitchfork bifurcation point), resulting in multiple steady-state solutions. The results are highly relevant in practice, as industrial columns usually have inputs on a mass or volume basis. The second type for specifications on a molar basis (e.g., molar reflux and molar boilup) depends on the presence of an energy balance in the model. The multiplicity is caused by interactions between flows and compositions in the column.
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    AIChE Journal 37 (1991), S. 547-554 
    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 interstitial pressure buildup and the internal stresses on the skeleton of a cylindrical green body during burnout are analyzed numerically. The intrinsic kinetics of pyrolysis is coupled with the Carman-Kozeny equation or the slip-flow model of Wakao and Smith to evaluate the pressure distribution. The stress distributions before failure are estimated from elasticity theory. The stresses are tensile, and their maxima are located at the center of the cylinder. The tangential stress is larger than the radial stress. The effects of green body size, specific surface area, and pressurized atmosphere are discussed. The approximate solution is accurate for small green bodies. The pressurized atmosphere reduces the interstitial pressure and the internal stresses effectively.
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    AIChE Journal 37 (1991), S. 617-628 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Recent advances in knowledge engineering have led to develop the qualitative (deep) model based diagnostic systems. As process knowledge accumulated, however, the diagnostic system remains strictly qualitative. This limits the usefulness of such systems. In this work, a framework is developed for integrating quantitative process knowledge into the qualitative model. Once quantitative process information, e.g., steady-state gains, is available, it can be incorporated into the simplest qualitative process model called the signed directed graph. The quantitative process knowledge is described in terms of membership functions of fuzzy set theory. According to the measurement pattern, the truth values of a hypothesis (e.g., a fault origin) can be calculated based on the fuzzy logic. Consequently, the diagnostic resolution can be improved significantly. Furthermore, the proposed method becomes a strictly qualitative diagnostic system, if no quantitative information is available. A chemical reactor example illustrates the design and performance of the qualitative/quantitative model-based diagnostic system. The proposed approach can also be extended to the multiple-fault situations in a straightforward manner.
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    AIChE Journal 37 (1991), S. 641-649 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Ignition, extinction and autothermal behavior of surface and homogeneous oxidation reactions of CH4, NH3, and mixed NH3/CH4 fuel systems in air over resistively heated Pt foils was studied in an atmospheric pressure flow reactor. Also examined were the effects of varying fuel concentration on the ignition, extinction, and autothermal surface temperatures. Heterogeneous ignition occurred at ∼200°C for NH3 and at ∼600°C for CH4. The mixed fuel systems exhibited two surface ignitions (∼200°C and ∼600°C), implying a sequential ignition of the two fuels. The effects of removing one of the fuels during autothermal operation gave results consistent with this hypothesis.In homogeneous ignition, two types of flames were observed: a boundary layer flame associated with NH3 systems and an independent flame observed in all systems. Homogeneous ignition of the two fuels and the mixtures occurred at surface temperatures ranging from 1,100°C to 1,600°C and appeared to be dominated by CH4 in the mixed systems. A generic behavior is proposed for homogenous-heterogeneous combustion of single and mixed fuels.
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    AIChE Journal 37 (1991), S. 679-686 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: High-surface-area, Zr-pillared, layered clays are synthesized and characterized for their adsorption properties. Although large free interlayer spacings are claimed in the literature (as also found in this work, 14.3 Å), the limiting pore size is the narrow interpillar spacing. The distribution of interpillar spacing is determined by molecular probing and adsorption data along with a theoretical framework available from the literature. Interpillar spacing can be tailored by controlling the number density of pillars inserted during the ion exchange (oligomer inserting) step. The following variables in the ion exchange solution result in lowering the pillar density: higher pH, lower oligomer concentration, and introduction of competitive cations. By changing these variables, peak interpillar spacing is shifted by nearly 2 Å (from 5 to 7 Å). The versatility of pillared clays as sorbents for kinetic separation (i.e., separation based on diffusivity differences) has been demonstrated by the separations of air and xylene isomers.
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    AIChE Journal 37 (1991), S. 769-779 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Adsorption of air in 5A zeolites was studied using Monte Carlo simulations in the grand canonical ensemble (μ, V, T constant). Site-site potentials were used to model the adsorbate-zeolite and adsorbate-adsorbate interactions. The potential model contains one adjustable parameter that was fit to a single experimental isotherm data point. Adsorption isotherms and heats of adsorption were determined for pure argon, oxygen, and nitrogen at 203.15 K, 233.15 K, and 297.15 K from 0.1 bar to 4.0 bar. Multicomponent adsorption isotherms were determined for binary mixtures of oxygen and nitrogen at 203.15 K. The results for the pure-component isotherms are in excellent agreement with experimental data. The results for the heat of adsorption are in good agreement with experimental data for argon and oxygen, but not for nitrogen. The results for multicomponent adsorption isotherms are qualitatively correct; however, the simulation was not able to quantitatively predict mixture data.
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    AIChE Journal 37 (1991), S. 836-844 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Equilibrium adsorption data for the N-benzoyl derivatives of D- and L-phenyl alanine in water/propanol solutions have been determined on a chiral-selective stationary phase, bovine serum albumin immobilized on silica. These data are well accounted for by an isotherm equation resulting from the sum of two Langmuir terms. The first term corresponds to the chiral-selective interactions, and the second to the nonselective molecular interactions between the enantiomers and the stationary phase. The individual band profiles of the two enantiomeric amino acids, either pure or in binary mixtures of various compositions, are predicted exactly by an equilibrium dispersive model using this bi-Langmuir isotherm. A classical Langmuir isotherm fails to predict these band profiles, illustrating the importance to collect accurate adsorption data and to use a correct isotherm model when calculating chromatographic band profiles.
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    AIChE Journal 37 (1991), S. 871-885 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Waxy crude oils are highly non-Newtonian materials known to cause handling and pipelining difficulties and whose flow properties are time- and history-dependent. Experimental techniques are described that enable reproducible steady-state flow property data to be obtained from rotational viscometers. The flow properties are shown to depend strongly on the shear rate applied during cooling (shear history effect). This leads to a definable minimum operating point below which flow in a waxy crude oil pipeline would cease. Modified pipeline design techniques are presented for both laminar and turbulent flow at temperatures below the pour point, and it is shown that existing techniques overestimate the flow rate in laminar flow by the order of 100%. The modified design techniques can be used to quantitatively assess the performance of flow improver (pour point depressant) additives under steady-state conditions.
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    AIChE Journal 37 (1991), S. 915-922 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Direct conversion of methane into higher hydrocarbons (ethane, ethylene, and to small extent C3-4 hydrocarbons) by its partial oxidation with oxygen in the absence of catalyst has been investigated. It was carried out in a quartz flow reactor at atmospheric pressure under nonflame conditions at different temperatures (1,123-1,273 K), CH4/O2 ratios (1.7-9.0), space velocities (500-5,000 h-1), and water concentrations (0.0-80 mol %) in the feed. No coke deposition was observed in the reactor, but there was a formation of small amounts of tarry matter in the reaction at ≥ 1,223 K, particularly for the lower CH4/O2 ratios (≤3.5). The product distribution in the process was strongly influenced by the dilution of feed with N2 or water. Addition of water in the feed was highly beneficial to obtaining higher yield and/or to selectivity for the higher hydrocarbons and suppressing almost completely the formation of tarry matter.
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    AIChE Journal 37 (1991), S. 953-954 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 37 (1991), S. 961-961 
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    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 37 (1991), S. 931-943 
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    Keywords: Chemistry ; Chemical Engineering
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    Notes: An important application of the recently developed techniques in qualitative mathematical modeling is to qualitatively predict how changes in the operation of chemical units affect their behavior. Weld (1987, 1988a,b) has developed a series of comparative techniques that analyze the effect of perturbations to the parameters of a given qualitative unit model. In this article we demonstrate a system, based on the qualitative process theory of Forbus (1984), which extends comparative analysis in two ways. First, it predicts the effects of changes in the qualitative equations and in parameter values. Secondly, it compares physical descriptions, rather than comparing models directly, and builds and compares the associated models automatically.
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    AIChE Journal 37 (1991), S. 955-957 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 37 (1991), S. 963-985 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The onset of three-dimensional reaction-driven convection in a porous medium is investigated using linear stability theory. The geometries investigated include a finite cylinder and a rectangular parallelepipped of arbitrary aspect ratios. The analysis determines, among other things, the likely modes (flow patterns) to emerge first as a function of reaction parameters and aspect ratios. The flow fields corresponding to three-dimensional modes are described in detail. Important qualitative differences are found between reaction-driven convection and the standard Lapwood or Bénard convection due to a temperature gradient applied to the boundaries of the system.The second part of the work examines numerically reaction-driven natural convection in a porous two-dimensional rectangular box. Orthogonal collocation and continuation techniques are used to determine the conduction and convection branches of solutions as a function of the Rayleigh number (Ra), the Frank-Kamenetskii number (δ) and the aspect ratio (α). The convective solutions (streamlines and isotherms) corresponding to primary, secondary and tertiary bifurcations are presented. The effect of natural convection (Ra) on the ignition point (critical δ value) is determined for three different aspect ratios.
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    AIChE Journal 37 (1991), S. 1027-1034 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A theoretical model comprising the processes of micropore, macropore and surface diffusion was derived and applied to the dynamics of adsorption of CO2 on a single activated-carbon particle. The effects of a nonlinear isotherm (Langmuir), particle nonisothermality and concentration dependence of the surface diffusivity were also incorporated. The theoretical model was fitted to a preliminary set of adsorption experimental data (two particle sizes, and various temperatures and concentrations) to determine the diffusion coefficients. The validity of the theoretical model was checked by using the model, with fitted diffusivities, to simulate dynamic adsorption curves at conditions different from those of the preliminary fitting data set. These model simulations were found to predict the experimental data in a satisfactory manner.
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    AIChE Journal 37 (1991), S. 1333-1340 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In chromatographic separations involving elutes with large differences in the molecular size, the adsorption saturation capacities of the elutes may differ because of the differences in the degree of size exclusion. With uneven saturation capacities, isotherm crossovers may occur, which often results in selectivity reversal. In this work, a new multicomponent isotherm has been developed for this kind of system. The isotherm is an extension of the common multicomponent Langmuir isotherm and introduces no or a very limited number of new parameters for its construction. The isotherm crossover conditions have also been derived. Simulations based on a general rate model using the new isotherm have successfully demonstrated the phenomena of peak reversal and crossover of breakthrough curves.
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    AIChE Journal 37 (1991), S. 1589-1592 
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    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 37 (1991), S. 1601-1606 
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    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Oscillations of a conducting drop immersed in a dielectric fluid in an alternating electric field were modeled to understand the enhancement of transport processes by the electric field. Numerical solutions for oscillation amplitude, velocity distribution, resonant frequency and streamlines were obtained. The effects of viscosity and density on the resonant frequency and the velocity distribution were investigated. It was found that the resonant frequency of viscous fluids was always smaller than the free oscillation frequency of the same droplet. The predicted scanning frequency response curve and the streamlines agree well with the experimental observations.
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    AIChE Journal 37 (1991), S. 1415-1419 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 37 (1991), S. 1459-1470 
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    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A direct numerical simulation (DNS) code has been modified to investigate chemically reacting flows in a stationary, homogeneous turbulence. Single and multispecies reactions as well as complicated reaction schemes such as parallel/consecutive reactions are studied. The effects of some parameters are discussed. The numerical data are used to test a simple first-order closure model, proposed by Dutta and Tarbell (1989), for turbulent reacting flows. It is shown that the DNS technique provides us with an effective tool to isolate the effects of different parameters and is likely to be useful for proposing and testing closure models.
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    AIChE Journal 37 (1991), S. 1737-1738 
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    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 37 (1991), S. 1749-1752 
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    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 37 (1991), S. 1780-1788 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Most existing criteria for predicting parametric sensitivity or runaway in a catalytic reactor are based on a single-phase model that does not account for interparticle heat and mass transfer resistances and intraparticle diffusion. Accounting for these effects, the simple criterion \documentclass{article}\pagestyle{empty}\begin{document}$$\frac{E}{{RT_f }}\frac{{(- \Delta H)r(T_f,C_f)}}{{T_f }}\left[{\frac{{d_t }}{{4U}} + \frac{{d_p }}{{6h}}} \right] 〈 0.368f(\phi _0)$$\end{document} defines the boundary of operating conditions, in which a catalytic reactor is insensitive to small perturbations. Here, r(Tf,Cf) is the intrinsic reaction rate at inlet conditions, dt(dp) and U(h) are the diameter of reactor tube (catalyst particle) and heat transfer coefficient between the fluid and tube wall (catalyst particle), respectively. The function f(φ0), where φ0 is the normalized Thiele modulus at inlet conditions, accounts for the effects of intraparticle diffusion. For the common case of equal coolant and feed temperatures, f(φ0) = 1 for φ0 〈 0.5 and f(φ0) = 2 φ0 for φ0〉0.5. The conservatism associated with the above criterion is comparable to the uncertainty involved in determining the parameters of the packed bed.
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    AIChE Journal 37 (1991), S. 1595-1597 
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    AIChE Journal 37 (1991), S. 1905-1905 
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    AIChE Journal 37 (1991), S. 1875-1894 
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    Keywords: Chemistry ; Chemical Engineering
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    Notes: Pure fluids and mixtures of species that hydrogen bond behave differently from systems that interact only through dispersion forces. The deviations from classical behavior often are sufficiently large that conventional equations of state and activity models cannot be used without the introduction of large, condition-dependent empirical parameters. Consequently, three different classes of theories have been developed specifically to treat hydrogen-bonding systems. The first is based on the assumption that when molecules hydrogen-bond, they react to form new species and consequently is referred to as “chemical” theory. The second is based on lattice-fluid theory that is used to describe different types of specific interactions and is known as “quasi-chemical” theory. The last is based on the solution of integral equations using a potential function that mimics that of a hydrogen bond. It is shown here that these three approaches give essentially equivalent results. This allows one to relate the parameters in the perturbation theory to the equilibrium constant and hence greatly improves its utility for real systems. All three theories are compared with simulation data.
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    AIChE Journal 37 (1991), S. 367-376 
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    Keywords: Chemistry ; Chemical Engineering
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    Notes: Diamond-like carbon films have been deposited from ternary mixtures of butadiene, hydrogen and argon in a parallel plate plasma reactor at constant pressure and power. These films have been etched in O2 and CF4/O2 plasma discharges. A new linear relationship between the composition of the deposition gas mixture and a dimensionless number (EN) defined in terms of etch and deposition rates and the bias voltage during deposition has been derived. EN is a function of the ion flux during deposition. Electron-impact ionization processes are considered for relating the ion flux to the feed gas composition and ionization potentials. The etch and deposition rate data follow this linear relationship very well. The proportionality constant in this linear relationship varies with composition for CF4/O2 etching data. Film hardness and failure modes on silicon and glass substrates are also described.
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    AIChE Journal 37 (1991), S. 490-498 
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    Keywords: Chemistry ; Chemical Engineering
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    Notes: The development of a concentration gradient along the vertical axis of a column of quiescent solution is explained within the framework of nonequilibrium thermodynamics. The formulae derived enabled us to determine explicitly the concentration difference between two vertical levels in a liquid column and specific conditions under which the concentration profile is at equilibrium. The concept of solute cluster formation in a supersaturated solution is consistent with the presented theory although the theory itself does not provide any direct or indirect proof of the occurrence of clustering.
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    AIChE Journal 37 (1991), S. 539-546 
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    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The heat transfer to, and the resultant evaporation of, drops of a volatile liquid sprayed upward in an immiscible liquid flowing down in a vertical column are analyzed to enable calculation of the volumetric heat transfer coefficient in the column. For this analysis, a model is contrived that assumes no nucleation delay in initially monodispersed drops and a heat transfer to each of the drops, with simultaneous evaporation, that can be approximated by an empirical correlation for heat transfer to an isolated drop evaporating in a quiescent, sufficiently extended medium. The expression obtained for the volumetric heat transfer coefficient is used to predict its values under some particular column operating conditions, which are then compared with relevant experimental data found in the literature.
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    AIChE Journal 37 (1991), S. 581-588 
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    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: We have shown that ionomeric membranes of perfluorosulfonic acid (PFSA) polymer allow selective pervaporation of polar organic compounds from their azeotropic mixtures with less polar compounds. A composite membrane of a thin PFSA polymer film, cast on a porous Teflon support, provided desirable permeant fluxes with good selectivity. Model binary azeotropes, composed of alcohols and hydrocarbons, were separated with total pervaporation fluxes of up to 9.5 kg/h·m2 using a stirred membrane permeation cell, the product side of which was exposed to vacuum. Fluxes increased with increasing alcohol content of the feed and with temperature. But the selectivity of the more permeating component remained reasonably constant around the azeotropic point and also over the range of temperature used in the study (25-55°C). Total pervaporation fluxes depended little on downstream pressure up to 6.66 kPa (50 torr). These separation data were explained by a mathematical model based on a solution-diffusion mechanism.
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    AIChE Journal 37 (1991), S. 607-616 
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    Keywords: Chemistry ; Chemical Engineering
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    Notes: The distribution coefficients of the solutes (toluene, naphthalene, and phenanthrene) are reported at infinite dilution between silicone rubber and supercriticalfluid carbon dioxide. A new technique is described in which a thin film of polymer is coated and cross-linked onto silica, and the distribution coefficient is measured rapidly by elution supercritical-fluid chromatography. Because CO2 significantly enhances the solute's volatility and its diffusion coefficient in the polymer, it is possible to study solute-polymer interactions at room temperature for nonvolatile compounds which would be difficult to study by conventional techniques such as gas chromatography. These infinite dilution data are used to determine solutepolymer interaction parameters to calculate phase diagrams over a wide concentration range. The residual, combinatorial, and cross-link contributions to the solute activity coefficient in the polymer are discussed as a function of concentration. In addition, pronounced pressure and temperature effects are described in terms of experimentally measured solute partial molar volumes (to - 14 L/mol) and partial molar enthalpies (to - 850 kJ/mol) in the fluid phase.
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    AIChE Journal 37 (1991) 
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    AIChE Journal 37 (1991), S. 705-723 
    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 major difficulty in control of distillation columns stems from their nonlinear behavior, especially of columns producing high-purity products. Based on a previous development that adapted fixed-bed theories to simple countercurrent processes, this study has established a nonlinear wave theory for the nonlinear and distributed dynamics of binary distillation columns by including the effects of reflux, reboil, and combination of sections. This theory clearly elucidates the intriguing dynamic behavior of distillation columns such as high steady-state gains, large response lags, strong dependence of dynamics on the magnitudes and directions of disturbances, and asymmetric dynamics of the transitions between two steady states. It also underlines the inadequacy of conventional linearized models for high-purity columns. With fairly simple mathematics, this nonlinear wave approach may be useful for model development, control system design, dual-composition control, and feedforward control.
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    AIChE Journal 37 (1991), S. 687-693 
    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 familiar batch concept of extent of reaction is reexamined for systems of reactions occurring in open systems. Because species concentrations change as a result of transport processes as well as reactions in open systems, the extent of reaction has been less useful in practice in these applications. It is shown that by defining the extent of the equivalent batch reaction and a second contribution to the extent of reaction due to the transport processes, it is possible to treat the description of the dynamics of flow through porous media accompanied by many chemical reactions in a uniform, concise manner. This approach tends to isolate the reaction terms among themselves and away from the model partial differential equations, thereby enabling treatment of large problems involving both equilibrium and kinetically controlled reactions. Implications on the number of coupled partial differential equations necessary to be solved and on numerical algorithms for solving such problems are discussed. Examples provided illustrate the theory applied to solute transport in groundwater flow.
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    Notes: Uniform submicron crystals of B4C, boron-enriched boron carbide, and B4C/TiB2 composite powders have been synthesized continuously by rapid carbothermal reduction at approximately 2,200 K in a 0.14 m ID × 1.68 m long pilot-scale graphite transport reactor. A unique reactor design allowed for continuous feeding of a meltable boron oxide containing precursor, rapid heating rates that completed the carbothermal reduction reaction in seconds, and an expanded cooling that allowed for the precipitation in space of volatile excess boron oxides. Powder morphology resembled that of powder synthesized by laser pyrolysis of gaseous reactants. Rapid heating rates and minimized reaction times at high temperatures promoted nucleation with limited crystal growth. Dense parts fabricated from these powders had fine grains and extreme hardness.
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    AIChE Journal 37 (1991) 
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    Keywords: Chemistry ; Chemical Engineering
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  • 169
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    AIChE Journal 37 (1991), S. 845-854 
    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 catalytic activity, product selectivity, and coke deposition were studied during methylcyclopentane (MCP) reforming on bifunctional Pt/Al2O3—Cl reforming catalysts with different metal loadings, but constant metal dispersion as well as constant Cl loading. Surprisingly, the overall conversion of MCP was found to decrease as the metal content of the catalyst increased. Analysis of the coke by temperature programmed oxidation (TPO) revealed two distinct peaks, one associated with coke on the metallic function and the other associated with coke on the acidic function. The change of activity of the metal and acid functions with time was monitored by following the rates of hydrogenolysis and hydrocracking, respectively. A mechanistically-based dual-site model for the kinetics of coke formation and the resulting deactivation was developed. The model successfully correlates the experimental data and is an improvement over existing models, since it explicitly accounts for the deactivation of both the metal and the acid functions.
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    AIChE Journal 37 (1991), S. 886-896 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Operational problems are of increasing importance as the process industries turn to the batch manufacture of high-value specialty products. A method is presented to minimize stockout for multiunit plants where customer orders may constitute nonintegral batch multiples. Product- and unit-dependent processing times and batch sizes, sequence-dependent changeover times, and product-to-unit assignment constraints are modeled for nonidentical parallel processes. Arbitrary initial conditions are also modeled. The algorithm determines the number of production runs of each product, run length (lot sizing), the assignment of run to units, and run sequence on each unit.Scheduling with simultaneous lot sizing has not previously been addressed in the literature. The evolutionary method presented here obtains near-optimal (and often globally optimal) solutions on industrial-sized test problems. These results are significant since near-optimal scheduling of many industrial process plants now becomes possible, although problems of this complexity are intractable using exact methods.
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    AIChE Journal 37 (1991), S. 923-930 
    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 spherical pore model for calculating the zeolite cavity radius and the potential energy of interactions of noble gases (Ar, Kr, Xe) is presented. The model utilizes the gas adsorption isotherm and equates the free energy change upon adsorption to the potential energy of interaction of the gas molecules with the zeolite cavity. The results obtained for the cavity radius using Ar, Kr, and Xe adsorption isotherms are in excellent agreement with those of the cavity radius for 5A, 13X, and Y zeolites obtained from crystallographic data. Also, the average potential energies of interaction of these gases with the surface atoms of the zeolite cavities, calculated from the isotherms and the spherical pore model, compare reasonably well with the internal energies determined from the experimental heats of adsorption.
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    AIChE Journal 37 (1991), S. 944-950 
    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 fluid extraction (SCFE) for the removal of organic toxins from water has been studied using a continuous-flow view cell system. Distribution coefficients (ratio of mole fraction of contaminant in supercritical CO2 to mole fraction in the aqueous phase at equilibrium) have been determined for a homologous series of contaminants as individual components in pure water: benzene, phenol, p-chlorophenol, and m-cresol. Data were obtained at two temperatures (313 and 323 K) and over a pressure range of 9.65 to 17.23 MPa for each contaminant. The distribution coefficients of the contaminants follow a pattern that can be explained in terms of molecular interactions both with water in the aqueous phase (as quantified by the pure contaminant solubility in water) and with CO2 in the SCF phase (as quantified by the pure contaminant solubility in near-critical CO2 and crossover phenomena in SCF CO2). These results have been accurately modeled using a hardsphere, perturbation-theory-based Carnahan-Starling-DeSantis-Redlich-Kwong equation of state and simple van der Waals mixing rules.
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    AIChE Journal 37 (1991), S. 1561-1570 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Formation of titania particles by vapor-phase oxidation of titanium tetrachloride was studied in an aerosol reactor between 1,200 and 1,723 K. The effect of process variables (reactor residence time, temperature, and reactant concentration) on powder size and phase characteristic was investigated using the differential mobility particle sizer, scanning electron microscopy, and X-ray diffraction. Titania particles were primarily anatase though the rutile weight fraction increased with increasing reactor temperature. The geometric number average diameter of the particles was between 0.13 and 0.35 μm, and the geometric standard deviation of the particle size distribution was about 1.4. The average particle size increased with increasing temperature, inlet TiCl4 concentration, and residence time. The observed changes in the particle size distribution were compared with those predicted by solving the aerosol dynamic equation by a sectional method and accounting for coagulation and first-order chemical reaction. While variations in the process variables resulted in discernible changes in the size of the particles, the spread of the distribution remained rather unaffected.
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    AIChE Journal 37 (1991) 
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    AIChE Journal 37 (1991), S. 1607-1612 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Random pore models have been successful in interpreting a wide range of experimental observations in gas-solid reactions; however, their applicability has been limited to cases where the entire porous structure is initially accessible to reacting gases. In many practical cases, porous solids contain significant void regions that are initially inaccessible to gaseous reactants, but become accessible in the course of the reaction. A conceptual and mathematical model is developed here that accounts for the existence of this hidden porosity. It uses the same representation of the porous network as was developed in the earlier random pore models, but introduces physically meaningful expressions for the discovery of hidden pores, and the subsequent growth of the discovered pores. The modified model calls for only one additional parameter, the initial volume fraction of hidden porosity in the total volume. It is demonstrated computationally that neglecting hidden porosity can lead to serious underestimations of conversion and reaction rates.
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    AIChE Journal 40 (1994), S. 380-380 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 40 (1994), S. 381-381 
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    AIChE Journal 40 (1994), S. 383-383 
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    AIChE Journal 40 (1994), S. 407-418 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A population-balance-equation model is employed for the analysis of liquid-liquid extraction columns. This model considers drop breakage, coalescence, and exit phenomena for the drop phase caused by drop-drop and drop-continuous phase interactions. Drop breakage and coalescence rates are employed from a previous study on liquid dispersions in stirred-tank contactors. A drop exit frequency is developed based on a stochastic modeling approach. The model is tested by drop size distribution and dispersed-phase volume fraction (holdup) data obtained for a multistage column contactor of pilot-plant scale. Steady-state drop size distribution and transient holdup measurements are obtained by a photomicrographic technique and an ultrasonic technique, respectively. The model can predict flooding of the column. The effect of mass transfer on the hydrodynamic parameters of the contactor is also examined. The population-balance-equation model can be used for the control of extraction columns and can be extended to include mass-transfer calculations for the prediction of extraction efficiency.
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    AIChE Journal 40 (1994), S. 586-593 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A dynamic model of a seeded batch crystallizer is used to investigate the process-dependent aspects of nucleation and growth kinetic parameter estimation by computer simulation. The satisfactory identification of all parameters in power-law-type kinetics with respect to supersaturation requires the use of nonlinear parameter transformations. The proper choice for transformation is problem-dependent, becoming more sensitive as nucleation rates increase, and the percentage of crystals below the measurable range increases.
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    AIChE Journal 40 (1994), S. 606-612 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Influence of local voids on flow maldistribution in randomly packed fiber bundles is examined by Voronoi tessellation. A theoretical expression for the local void distribution caused by random placement of fibers is developed by using a randomcell model. Simulations and packing experiments have been conducted to assess the accuracy of the theoretical distribution of cell sizes. In the case of shell side, laminar flow parallel to the fibers, the theoretical distribution is used to estimate fRe (friction factor times Reynolds number) and volumetric flows, and to compare results with ordered arrays and experimental data from literature. The results are used to assess the contributions of local voidage variation to flow bypass. This has implications for the prediction of pressure drop and heat and mass transfer in hollow-fiber module applications where transport is dominated by flow on the shell side.
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    AIChE Journal 40 (1994), S. 621-626 
    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 use of polar hydrotropes in extractive and in liquid-liquid extraction has been extensively reported in the literature. In this article, the effect of hydrotropes on increasing the effectiveness of separation is explained in terms of the effect of the dipole-induced dipole and the ion-induced dipole interactions on the activity coefficients of the neutral solutes in the aqueous phase. The self-consistent local composition theory is used to correlate quantitatively the observed behavior in systems involving liquid-liquid equilibria. The theory yields composition-dependent expressions for the effect of each independent pair interaction on the activity coefficient of a neutral solute in the aqueous phase. The ratio of the activity coefficients of the two solutes is of interest in this context. The resulting expression for the separation factor is elegant and admits simple physical interpretation. The essential features of hydrotrope-assisted extraction are correctly described by the theory. The ability of the theory to correlate data is demonstrated for two systems.
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    AIChE Journal 40 (1994), S. 647-669 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: This article concerns general multivariable nonlinear processes, particularly those with singular characteristic matrix. A precise characterization of the structural process properties that give rise to generic singularity of the characteristic matrix is initially developed within a graph-theoretic analysis framework. An output feedback controller synthesis problem is then formulated for multivariable processes with singular characteristic matrix. A comprehensive solution to this problem is obtained through a combination of dynamic state feedback controllers and state observers. The performance and robustness characteristics of the proposed control methodology are illustrated through simulations in a double-effect evaporator.
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    AIChE Journal 40 (1994), S. 676-691 
    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 semiempirical thermodynamic method is developed to establish a framework for calculating vapor-liquid and liquid-liquid equilibria in ternary systems containing water, an organic solvent, and a salt. Careful attention is given to precise definition of standard states. Short-range ion-solvent forces are taken into account primarily by a chemical-equilibrium method based on stepwise ion solvation; however, physical contributions also contribute. Water-cosolvent nonideality is described by an extended equation of the van Laar form. Long-range electrostatic forces between ions are taken into account by an extended Debye-Hückel equation with corrections for transferring from a McMillan-Mayer to a Lewis-Randall framework.The new method is illustrated with results for several systems including saturated aqueous mixtures of LiBr or LiCl with methanol where the salt concentration exceeds 20 molal. The method developed here is of particular interest for process calculations in extractive crystallization, a low-energy operation for producing salt from aqueous solution.
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    AIChE Journal 40 (1994), S. 704-715 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Chemotaxis describes the ability of motile bacteria to bias their motion in the direction of increasing gradients of chemicals, usually energy sources, known as attractants. In experimental studies of the migration of chemotactic bacteria, 1-D phenomenological cell balance equations (Rivero et al., 1989) have been used to quantitatively analyze experimental observations (Ford et al., 1991; Ford and Lauffenburger, 1991). While attractive for their simplicity and the ease of solution, they are limited in the strict mathematical sense to the situation in which individual bacteria are confined to motion in one dimension and respond to attractant gradients in one dimension only. Recently, Ford and Cummings (1992) reduced the general 3-D cell balance equation of Alt (1980) to obtain an equation describing the migration of a bacterial population in response to a 1-D attractant gradient. Solutions of this equation for single gradients of attractants are compared to those of 1-D balance equations, results from cellular dynamics simulations (Frymier et al., 1993), and experimental data from our laboratory for E. coli responding to α-methylaspartate. We also investigate two aspects of the experimentally derived expression for the tumbling probability: the effect of different models for the down-gradient swimming behavior of the bacteria and the validity of ignoring the temporal derivative of the attractant concentration.
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    AIChE Journal 40 (1994), S. 716-725 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Two methods for generating smoothing splines are compared and applied to data from a fed-batch fermentation process. One method chose both the degree of the spline and its parameters by minimizing the generalized cross validation (GCV) function using a genetic algorithm (GA). The other method adjusted the smoothing spline to a specified chi-square goodness-of-fit, requiring prior knowledge of the measurement variability. The GCV/GA method led to excellent results with all the fermentation data records. The goodness-of-fit method gave a family of spline fits; splines with a low percentage fit extracted trends from the data, while for general use a 50% fit appeared satisfactory. The goodness-of-fit method executed more quickly than the GCV/GA method, but the GCV/GA method was more generally applicable as it chose both the degree of the spline and the amount of smoothing automatically.
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    AIChE Journal 40 (1994), S. 738-738 
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    AIChE Journal 40 (1994), S. 738-739 
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    AIChE Journal 40 (1994), S. 1-1 
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    AIChE Journal 40 (1994), S. 2-10 
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The coating flow of a reactive fluid on an inclined plane is studied. The fluid viscosity steadily increases due to a sustained cross-linking reaction. Using well-known long wave approximations and a simple kinetic relation, we find that the linear stability of a uniform coating is affected not only by the inclination angle but also by the reaction order. In the weakly nonlinear limit, a generalized Kuramoto-Sivashinsky (K-S) equation is derived. Two interesting cases are identified in the limit of creeping flow. One is when surface tension is moderate and a generalized Burger's equation results, and the other is when the surface tension is large and the traditional K-S equation is recovered when the inclination angle is greater than 90°. The solution in this case represents a shock-like traveling wave down the incline and it appears to be unique for reacting coating flows.
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    AIChE Journal 40 (1994), S. 11-18 
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    Notes: The dynamic evolution of the cluster-size distribution (CSD) in the precoalescence stages of nucleation and growth for sizes within and beyond the nucleation barrier layer (NBL) has been obtained. The existence of several universal kinetic laws of nucleation is predicted. In the precoalescence stages of nucleation, the CSD for sizes within and beyond the NBL obeys dynamic scaling relations. In a range of sizes beyond the NBL, the CSD exhibits a universal power law behavior, the exponent of which depends only on the interphase monomer transfer mechanism. Based on the results for the CSD, a general foundation is developed for nucleation kinetic measurements including the determination of the nucleation barrier and the inter-facial monomer transport rate by measuring the CSD. A preliminary comparison with an experimental study confirms the predicted dynamic scaling and the power law behavior of the CSD in the early stages of nucleation and growth.
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    AIChE Journal 40 (1994), S. 19-28 
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    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A theoretical model for the process of bubble and drop formation in flowing liquids, applicable for both terrestrial and microgravity environments, has been developed by using a force balance. The contact angle variation at the nozzle due to the bubble motion and the added mass coefficient of the bubble moving through a pipe have been theoretically analyzed, considering bubble motions during its expansion and detachment stages. Predictions of bubble size of the model show satisfactory agreement with available experimental results in the case of normal gravity. The effects of the nondimensional variables on bubble and drop size are evaluated in microgravity conditions. In microgravity, the bubble is detached from the nozzle only by the liquid flow drag, and in the region of low liquid velocity the bubble size becomes much larger than that in normal gravity.
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    AIChE Journal 40 (1994), S. 756-766 
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    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The falling liquid film has become a popular means of transferring heat and mass from a vapor to a binary liquid, especially in gas-fired heat pump systems. Ideally, the required amount of heat and mass transfer can be accomplished by using a simple cylindrical tube; however, increasingly stringent size and weight requirements for the machine prohibit use of the simple cylindrical surface, and other more complex surfaces with higher absorption capacities have been sought. In this article, absorption of a single component and condensation of a binary mixture on an axially fluted tube is considered. The solution to the problem hinges on the energy equation, although the entire energy transfer process is mass-transfer-limited. Significant mass transfer is limited to a thin layer near the liquid-vapor interface. Solutions to the energy equation are obtained for both the conduction- and convection-dominated regimes. In the latter, significant heat transfer occurs within a thin layer near the liquid-vapor interface which contains the mass transfer layer; this “boundary layer” structure does not appear to have been recognized in previous work in this area. Using the present results, the capacity of a given tube may be predicted as a function of governing geometrical and physical parameters. The principal objective of this work is to develop the theoretical tools from which computations may be carried out during a design process. The theoretical results may be applied to mixtures typical of application in the absorption heat pump industry.
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  • 197
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    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 40 (1994), S. 786-798 
    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 new approach for developing fundamental equations of oxygen permeation through thin mixed-conducting oxide ceramic is presented considering both surface reactions on membrane-gas interfaces and the diffusion of charged species in the bulk oxide. The essence of this work is the coupling of surface reactions with the bulk diffusion using a novel approach which differs from the conventional Wagner. Theory applicable only to limited cases. With this approach, fundamental equations based on various permeation mechanisms can be derived for oxygen permeation through thin mixed-conducting oxide membranes, which is impossible using conventional approach. In general, the final results are a complex implicit equation correlating the oxygen permeation flux to the driving force, membrane thickness, and rate constants with physical significance in each step. Somewhat simpler theoretical oxygen permeation equations are obtained for some special cases (mixed-conducting membranes with a rate-limiting step, ionic-conducting membranes, ionic-conducting membranes with a reducing agent in permeate side). Theoretical results derived using this new approach agree excellently with the experimental oxygen permeation data. It is theoretically and experimentally shown that for ionic conductors, the surface permeation parameter measured by the dynamic permeation method is directly related to the oxygen isotope exchange rate constant measured under equilibrium conditions.
    Additional Material: 5 Ill.
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  • 198
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 40 (1994), S. 826-838 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Schemes for monitoring the operating performance of large continuous processes using multivariate statistical projection methods such as principal component analysis (PCA) and projection to latent structures (PLS) are extended to situations where the processes can be naturally blocked into subsections. The multiblock projection methods allow one to establish monitoring charts for the individual process subsections as well as for the entire process. When a special event or fault occurs in a subsection of the process, these multiblock methods can generally detect the event earlier and reveal the subsection within which the event has occurred. More detailed diagnostic methods based on interrogating the underlying PCA/PLS models are also developed. These methods show those process variables which are the main contributors to any deviations that have occurred, thereby allowing one to diagnose the cause of the event more easily. These ideas are demonstrated using detailed simulation studies on a multisection tubular reactor for the production of low-density polyethylene.
    Additional Material: 10 Ill.
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  • 199
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 40 (1994), S. 849-861 
    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 systematic methodology applicable to the optimal design of stable process systems is presented. It is based on the formulation of a parametric problem that provides bounds on the optimal stable solution and an iterative algorithmic approach that attains convergence of the bounds in a finite number of iterations. The bounds on the optimal stable solution are based on analytical expressions of bounds on the eigenvalues of the Jacobian matrix using the concept of the measure of the matrix. When extended to the synthesis problem of reactor networks, the approach is able to couple the optimization problem with stability issues even in cases where the number of reactors is large and the reaction mechanism is described by a general complex reaction scheme. Furthermore, since at the synthesis level the reactor network represents an exhaustive superposition of the existing structural and operational alternatives, the approach fully exploits these alternatives and coordinates a weighted optimal search that improves the objective and accommodates a stable reactor network. This approach is not restricted to the synthesis of reactor networks and can be applied to the design of total process flowsheets.
    Additional Material: 9 Ill.
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  • 200
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 40 (1994), S. 870-877 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Oxidative coupling of methane was conducted by using membrane reactors. The nonporous membrane film that consisted of PbO modified by alkaline or alkaline earth compound was supported on porous SiO2-Al2O3 tube. Higher hydrocarbons were successfully synthesized with high selectivity (about 90%). A kinetic analysis was conducted to clarify whether oxide ion transportation through PbO film participated in the oxidative coupling of methane. The evaluated value of the diffusion coefficient of oxide ion transport based on the methane oxidation agreed well with that of published data. The simulated gradient of the oxide ion concentration through the PbO membrane agreed well with that measured by electron probe X-ray microanalyzer. A transient response simulated by using kinetic parameters evaluated from steady-state analysis also agreed well with the experiment. These results prove the validity of the reaction model that consists of surface reactions of methane with oxide ion which is transferred from inside to outside of the membrane reactor. Alkali modifiers on the PbO membrane surface exhibited a promotional effect on the surface reaction of methane coupling. Another membrane reactor containing Bi2O3 showed higher activity than the PbO membrane.
    Additional Material: 17 Ill.
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