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  • 1995-1999  (3,021)
  • 1995  (3,021)
  • Analytical Chemistry and Spectroscopy  (1,554)
  • Engineering General  (737)
  • Chemical Engineering  (730)
  • Nuclear reactions
Material
Years
  • 1995-1999  (3,021)
Year
Keywords
  • 101
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 9 (1995), S. 139-141 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 102
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 9 (1995), S. 229-229 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 103
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 104
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 9 (1995), S. 309-322 
    ISSN: 0886-9383
    Keywords: simulated annealing ; messy genetic algorithms ; optimization of multimodal objective functions ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The method of simulated annealing is modified so that the concept of messy chromosomes is applied. Constituent genes of messy chromosomes are specified by their respective names (indices) and values (alleles) simultaneously. Unlike simple chromosomes (binary vectors), messy chromosomes may be either under- or overspecified with respect to the problem being solved. The messy simulated annealing algorithm is a very robust and efficient stochastic optimization method which is able to find correct minima of deceptive or highly multimodal objective functions. This is shown by way of a number of simulations.
    Additional Material: 7 Ill.
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  • 105
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 9 (1995), S. ii 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 106
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 9 (1995), S. 373-387 
    ISSN: 0886-9383
    Keywords: robust regression ; outliers ; spectroscopy ; calibration ; MASBR (maximum sum of binary coded residuals) ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In this paper, a novel robust regression method, the maximum sum of binary coded residuals (MASBR), is proposed. Instead of the sum of squared residuals used in least squares regression as the minimization criterion, MASBR regression maximizes the sum of binary coded residuals. MASBR regression is designed for cases where the conventional robust regression methods with breakdown points less than 50% fail. To circumvent the problem of being trapped in local optima, a stepwise-varying acceptable error limit (SVAEL) algorithm is proposed. Both numerical simulation and treatment of real analytical data demonstrate the feasibility of MASBR regression in conjunction with the SVAEL algorithm.
    Additional Material: 5 Ill.
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  • 107
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 9 (1995), S. 431-432 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 108
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 9 (1995) 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 109
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 9 (1995), S. 489-507 
    ISSN: 0886-9383
    Keywords: QSAR ; partial least squares ; robust regression ; CoMFA ; weighted regression ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A robust implementation of partial least squares (PLS) is developed in which the method of iteratively reweighted least squares is adapted for use with PLS. The result is a PLS algorithm which is robust to outliers and is easy to implement. Examples and case studies are presented, followed by two Monte Carlo studies designed to explore the behavior of the method.The paper begins with the motivation and intended applications for the procedure. A discussion is given of the method of interatively reweighted least squares (IRLS) for outlier detection. The procedure, given the name IRPLS, is then presented. Three case studies illustrate how the procedure works on various types of data and how it should be used. The first Monte Carlo study is designed to determine whether the IRPLS procedure correctly identifies multiple outliers in a wide variety of configurations. The second Monte Carlo study is designed to estimate the breakdown bound of the procedure.
    Additional Material: 6 Ill.
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  • 110
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 111
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 9 (1995), S. 31-58 
    ISSN: 0886-9383
    Keywords: Multivariate curve resolution ; Three-way data analysis ; Factor analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A new multivariate curve resolution method is presented and tested with data of various levels of complexity. Rotational and intensity ambiguities and the effect of selectivity on resolution are the focus. Analysis of simulated data provides the general guidelines concerning the conditions for uniqueness of a solution for a given problem. Multivariate curve resolution is extended to the analysis of three-way data matrices. The particular case of three-way data where only one of the orders is common between slices is studied in some detail.
    Additional Material: 15 Ill.
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  • 112
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 9 (1995), S. 179-195 
    ISSN: 0886-9383
    Keywords: GRAM ; PARAFAC ; rank overlap ; second-order calibration ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: GRAM, a method for second-order calibration, has been introduced by Sanchez and Kowalski and later modified by Wilson, Sanchez and Kowalski. The methods are based on the claim that, in cases without measurement error they yield correct estimates for the concentration ratios and profiles of (rank-one) analytes present in sample and mixture. This claim has not been proven rigorously. In the present paper, rigorous proofs are given for situations where the claims are valid indeed. In addition, it is shown that PARAFAC, an alternative method for second-order calibration, can be used to obtain the same results. Next it is shown that the claims do not hold in cases with ‘rank overlap’ (partly overlapping profiles) and it is proven that a procedure by Wang et al. can still be used to assess some of the concentration ratios. A general framework is provided for a variety of second-order calibration problems and the extent to which quantitative and qualitative information can be expected is given.
    Type of Medium: Electronic Resource
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  • 113
    Electronic Resource
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    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 9 (1995), S. 223-225 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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  • 114
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 9 (1995), S. 232-236 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 115
    ISSN: 0886-9383
    Keywords: multiway data ; standard addition method ; calibration ; matrix effects ; trilinear decomposition ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Presented here is an algorithm for analysis of second order data by the method of standard additions. The method of standard additions is applicable when matrix effects make traditional calibration unreliable. The algorithm employs a generalized eigenproblem to mathematically separate the instrument response of the analyte from the instrument response of any interfering species. A scheme for determining the eigenvectors (and hence the concentration estimate) that uniquely correspond to the analyte of interest is given. These eigenvectors can readily be distinguished from any eigenvector that corresponds to the spectrum of the interferents or both the interferents and analyte. The stability of the estimated analyte concentration is verified by Monte Carlo simulations. The algorithm is applied to the analysis of trichloroethylene in samples that have matrix effects caused by an interaction with chloroform.
    Additional Material: 12 Ill.
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  • 116
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 9 (1995), S. 327-328 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 117
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 9 (1995), S. 343-362 
    ISSN: 0886-9383
    Keywords: straight line calibration ; errors in both axes ; uncertainties ; linear regression ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Calibration is a fundamental step in the calculation of the unknown concentration of analyte in most analytical methods. It is known that for certain methodologies, if only the errors in the independent variable are taken into account, there may be considerable errors in the estimation of the value of the regression coefficients, the derived statistical parameters and in some cases the sought for response and concentration values. This paper reviews the calibration methods including some references to procedures for the detection of outliers and robust regression when there are errors in both axes. The advantages and limitations of the different approaches are discussed and a comparative study is made of the approaches of several techniques for which computer programmes have been developed based on the algorithms put forward by the different authors. Finally, some trends of future development in this field are envisaged.
    Additional Material: 2 Ill.
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  • 118
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 9 (1995), S. 411-422 
    ISSN: 0886-9383
    Keywords: gasoline ; classification ; multiple regression ; non-correlated variables ; accuracy of measurements ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A procedure for the classification of motor gasolines by their trend to carburettor icing has been proposed. For this goal a set of regression models was employed. Motor gasoline classification was carried out in terms of the isopropyl equivalent using seven physicochemical properties.
    Additional Material: 4 Ill.
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  • 119
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 120
    ISSN: 0886-9383
    Keywords: sequential response surface modelling ; Williamson ether synthesis ; SN2 ; optimization ; reaction kinetics ; reaction mechanism ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In this work the utility of a new method for determining kinetic parameters by sequential response surface modelling, previously described (Part 1), is shown by applying it to an experimental study of a reaction with known kinetics. The nucleophilic substitution reaction between ethoxide and benzyl chloride, the Williamson ether synthesis, was selected as a model reaction. This reaction is known to proceed with second-order kinetics. The method gives access to estimates of initial reaction rate which can be further used to obtain estimates of activation energy and reaction order of reactants. The results obtained are in good agreement with the estimated values of these parameters obtained with conventional kinetic experiments.
    Additional Material: 2 Ill.
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  • 121
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 9 (1995), S. 483-487 
    ISSN: 0886-9383
    Keywords: fractional factorial design ; multiresponse ; PLS ; PCA ; reduced-rank regression ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This paper presents an interpretation of PLS applied to orthogonal explanatory variables. In particular, it is shown that in fractional factorial multiresponse experiments PLS2 gives identical results to ordinary least squares applied to principal components of the response variables. The general relationship is that the reduced-rank regression algorithm which first projects Y onto the X-space and then truncates this matrix by principal component analysis before performing ordinary least squares estimation gives the same predictor as PLS2 and SIMPLS if all the non-zero eigenvalues of XTX are identical.
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  • 122
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 123
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 124
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 9 (1995), S. 531-531 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 125
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 9 (1995) 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 126
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 9 (1995) 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 127
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    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 9 (1995), S. 283-308 
    ISSN: 0886-9383
    Keywords: simulated annealing ; threshold acceptance ; wavelength selection ; selectivity ; optimization ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Simulated annealing (SA) is a stochastic search method that has been applied to combinatorial search problems in chemometrics. Unlike strict iterative improvement methods, SA tolerates temporary moves to detrimental parameter configurations during an optimization. The method used by SA to decide whether or not to accept detrimental steps is a special case of a more general acceptance rule. The present work investigates the performance of various SA-type algorithms that differ only in the acceptance rule for detrimental steps when optimizing continuous or discrete problems. A method for step width modulation is introduced to overcome the poor ability of SA type algorithms to locate the exact extreme of a function. The studied search strategies are modified for the discrete problem of wavelength selection. In order to evaluate SA-type algorithms and their abilities to deal with the wavelength selection problem, two global measures of selectivity are used as criteria to determine the most suitable wavelength subset that maximizes selectivity for pure component ultraviolet-visible spectra.
    Additional Material: 7 Ill.
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  • 128
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    Journal of Chemometrics 9 (1995), S. 329-330 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 129
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 130
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    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 9 (1995), S. 451-457 
    ISSN: 0886-9383
    Keywords: non-linear regression ; optimization ; robust methods ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Several robust regression methods, including a new proposal, are described and their properties discussed. Resistance to various types of outliers and non-normality is demonstrated. The techniques are applied to non-linear regression models from chemical kinetics and calibration. Optimization of the types of objective functions encountered when applying robust regression is considered.
    Additional Material: 5 Ill.
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  • 131
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    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 9 (1995), S. 471-481 
    ISSN: 0886-9383
    Keywords: batch prediction ; continuum regression ; multivariate calibration ; sequential prediction ; simultaneous prediction ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In analytical chemistry a single fitted calibration model is used repeatedly to predict the level of the analyte of interest for the specimens comprising the prediction set. Unlike the calibration (or training) set, which is often limited in size, the prediction set can be very large.In the case of multivariate calibration a number of methods such as PLS and PCR are commonly used to construct the calibration model. The set of instrumental measurements and the reference analyte level are available for each specimen in the calibration set. For specimens in the prediction set, only the instrumental measurements are available, since the problem is to predict the analyte level for these specimens. It is not widely recognized that predictions of the analyte levels for individual specimens can be improved by utilizing seemingly unrelated information from the instrumental measurements associated with the other members of the prediction set. In the case of PCR there exists a very straightforward procedure for doing this. A description of the various sources of prediction errors is provided to explain the ability of PCR to utilize this additional information. The use of PCR in this context is illustrated with both a synthetic and a real example.
    Additional Material: 1 Ill.
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  • 132
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995) 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 133
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 445-445 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 134
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 604-618 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: By “reverse engineering” the functions of a specific biological system, habituating control strategies are developed for process control applications. A habituating control system has the distinguishing property of more more manipulated inputs than controlled outputs; with the inputs differing significantly in their dynamic effect on the outputs and in the relative costs of manipulating each one. A habituating controller coordinates the use of all the available inputs to achieve high-performance output objectives while simulatneously minimizing the cost of taking control action.The “baroreceptor reflex,” the control system responsible for short-term blood pressure regulation, provides the biological paradigm for the analysis and design of the habituating control structure. Its main characteristics are discussed from a process control perspective, indicating that the robust, high-performance control, characteristic of biological systems is partly due to such habituating control architectures. The broad range of potential process applications is illustrated with two examples. Two basic strategies are presented for the design of habituating controllers for linear systems with two inputs and one output: the direct synthesis approach and the model predictive approach. Compared to previous techniques for multiple-input, single-output systems, the direct synthesis strategy is straightforward and systematic. Simulation results demonstrate the superior performance of habituating control compared to conventional techniques for which the number of inputs and outputs are equal.
    Additional Material: 18 Ill.
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  • 135
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 649-657 
    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 residence time distribution of the liquid phase within a three-phase monlith reactor is determined using tracer studies. The actual liquid residence time in the monolith, relevant for reactor design purposes, is calculated from overall residence time measurements using deconvolution by Fourier transform. The liquid-phase residence time decreases as liquid or gas flow rates increase, but the reactor Peclet number remains approximately constant. The residence time distribution and calculated values of the Peclet number reveal that the liquid phase is substantially well-mixed. Comparison with results from experiments in a single glass capillary reveals that the monolith channels become predominantly liquid-filled, particularly as the liquid flow rate becomes a significant fraction of the total flow rate.
    Additional Material: 13 Ill.
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  • 136
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 677-682 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Shear thinning of ternary microemulsions of didodecyldimethylammonium bromide (DDAB), water, and dodecane in the range 103 to 106 s-1 is documented over a wide range of compositions. A marked transition in the characteristic shear rate is observed accompanying the structural transition from bicontinuous to water-in-oil (w/o) droplets as previously reported from diffusion and small-angle scattering techniques. Results in the w/o region are consistent with those for a dispersion of hard spheres. The shear thinning of the bicontinuous structure, however, occurs at much higher shear rates, implying a shorter time and length scale for disruption of the equilibrium liquid structure by the flow field.
    Additional Material: 6 Ill.
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  • 137
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 666-676 
    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 comprehensive mathematical model for describing the process of dissolution of a spherical polymeric particle in a convective field is developed. It includes the process of glass transition, reptation of macromolecules, disengagement of these molecules from the gel-liquid interface, and diffusion in the boundary layer surrounding the gel-liquid interface. Different controlling regimes for the dissolution process are identified and quantitatively delineated in this moving boundary problem. Analytical solutions for the estimation of dissolution time for various limiting cases are presented. Key predictions from the model are verified by comparison with preliminary experimental data. A novel feature of a particle-size-independent dissolution of polymeric particles below a critical size brought out by the model is verified experimentally. The findings have pragmatic implications in diverse areas, such as polymerization, drag reduction, and microlithography.
    Additional Material: 9 Ill.
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  • 138
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 658-665 
    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 reactive ion etching kinetics of InP studied uses BCl3/Ar and BCl3/Ar/O2 as etchants. High-temperature etching using BCl3 and Ar increases the etch rate negligibly. However, the addition of 30% oxygen in the gas feed increases etch rates by a factor of 10,000 up to 1.5 micron/min at wafer temperatures of 250°C. X-ray photoelectron spectroscopy analysis reveals that oxygen removes the boron species adsorbing on the InP surface by scavenging the boron to form volatile boron oxides. To study the gas-phase chemistry, optical emission spectroscopy is used to monitor atomic chlorine intensity at different gas mixtures. The chlorine intensity shows a Gaussian-type dependence with oxygen addition, which is similar to the etch rate dependence. Two regimes of etching found are: at temperatures below 150°C, the etching is limited by the removal of indium chlorides; above 180°C, the etching is reaction-limited. The surface morphology shows that the etch profile becomes rougher as a result of increased chemical etching. At high power densities (0.21 W/cm2) and intermediate temperatures (150°C), near vertical wall shapes are obtained. A kinetic model for the high-temperature etching is developed, as well as a rate law based on the InCl formation reaction. The rate law compares favorably with experimental etch rate results.
    Additional Material: 11 Ill.
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  • 139
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 41 (1995), S. 683-690 
    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 cubic equation of state mixing rule of Wong and Sandler is reformulated in a way that eliminates one of its parameters and so that it can go smoothly from activity coefficient-like behavior to the classical van der Waals one-fluid mixing rule merely by variation of its parameters. The parameters in the reformulated mixing rule can be obtained from correlation of vapor-liquid equilibrium data or from the two infinite dilution activity coefficients for each binary pair in the mixture. When these activity coefficients are estimated from the UNIFAC group contribution model, the mixing rule becomes completely predictive. The correlative and completely predictive forms of this mixing rule are tested here and shown to be accurate for five difficult binary systems and one ternary mixture over large ranges of temperature and pressure.
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  • 140
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    AIChE Journal 41 (1995), S. 1099-1112 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Non-Newtonian fluid flow in porous media is encountered in a variety of applications. Aspects of single-phase flow of power-law fluids in porous media are examined. First, homogenization theory is used to derive a macroscopic law. It is shown that the single-capillary power law between flow rate and pressure gradient also applies at the macroscopic scale, provided that the Reynolds number is sufficiently small. Homogenization theory confirms the validity of the use of pore network models to describe flow of power-law fluids, although not necessarily of fluids of a more general rheology. Flow in pore networks is next used to explore various pore geometry effects. Numerical simulations show that approaches based on an effective medium or on the existence of a critical path, which carries most of the flow, are valid in narrow- or wide-pore-size distributions, respectively. The corresponding expressions agreed well with the numerical results in the respective ranges. An analysis presented for Bethe lattices leads to closed-form expressions in two limits: for an effective medium and near percolation. The behavior near percolation generalizes the results of Stinchcombe (1974) for the linear (Newtonian) case.
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  • 141
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    AIChE Journal 41 (1995), S. 1122-1134 
    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 mass transfer from a Newtonian fluid to a swarm of spheroidal adsorbers under creeping flow conditions is considered using the spheroid-in-cell model to represent the swarm. The flow field within the fluid envelope for the Kuwabara type of boundary conditions is obtained form the analytical solution of Dassios et al. (1994). The complete convective diffusion equation is used to describe mass transport within the envelope so that moderate and strong diffusional terms can be taken into account. A new set of boundary conditions is used that respects mass flux and concentration continuity across the outer surface of the cell and maximizes the applicability of the spheroid-in-cell model in the convection-to-diffusion transition regime. The resulting elliptic problem in two dimensions is solved numerically. Results for the upstream and downstream concentration profiles reveal that tangential diffusion is very significant and should not be neglected for moderate and low Peclet number values. Also, the classical Levich-type of formulation, which is theoretically valid for very weak diffusional terms only, can in practice be modified to predict with fair accuracy the overall Sherwood number and the adsorption efficiency of prolate and oblate spheroids-in-cell even in moderate Peclet number cases.
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  • 142
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    AIChE Journal 41 (1995), S. 1153-1164 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Filtration on horizontal surfaces facing upward is accompanied by sedimentation. Material balances that are based solely on the volume of filtrate and neglect sedimentation flux lead to an understatement of the solids deposited in the cake and potentially large errors in calculated values of the average specific resistance αav. In a gravitational sedimentation experiment with kaolin, the value of αav neglecting sedimentation was 3.75 times greater than the value including the effect of sedimentation. In addition to errors due to neglect of sedimentation, CATSCAN studies show that the slurry concentration above the cake increases with time, contrary to usual assumptions. In a manner similar to batch sedimentation in a closed cylinder, characteristics of constant composition arose from the cake surface. Approximate predictions based on a combination of traditional sedimentation and filtration theory were in accord with the CATSCAN data. Existing filtration theory must be substantially modified to account for the effect of sedimentation.
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  • 143
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    AIChE Journal 41 (1995), S. 1165-1170 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Cross-linked terpolymers of allyl acetylacetone, 2-hydroxyethyl methacrylate, and ethylene glycol dimethacrylate were synthesized in the oil phase of a bicontinuous microemulsion stabilized with didodecyldimethylammonium bromide. The resulting material is porous, with a surface area of 58 m2/dry g. It selectively adsorbs copper, picking up 0.07 meq/dry g from a 0.1-M solution. This is less than the total apparent capacity of 0.65 meq/dry g inferred from titration with base and much less than the amount in conventional, nonselective resins, which is typically 5 meq/dry g. Breakthrough curves in packed beds and across membranes of this material seem consistent with uptake controlled by chemical reaction compromised by dispersion. Nonporous membranes of this material do not show facilitated transport.
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  • 144
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    AIChE Journal 41 (1995), S. 1171-1183 
    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 general numerical method is developed for multicomponent chromatography for the case where a pH gradient occurs and several buffering species are present that become adsorbed together with the components being separated through an ion-exchange mechanism. Acid-base equilibrium relations are used to determine the ionic compositions in the liquid and adsorbed phases and are solved using a single-variable Newton's method. The differential material-balance relations are integrated numerically using the method of characteristics. The transport relations are incorporated using a matrix analog of the linear-driving-force approximation. The resulting method accounts for the adsorption of each ionic form of each buffering species, for multicomponent diffusional interactions arising from induced electric fields, for volume and concentration overloading of proteins, and for changes in the adsorption capacity caused by pH variations. Numerical calculations illustrate factors govening the selection of the adsorbent and buffer components for use in separating mixtures of proteins using retained, internally generated pH gradients.
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  • 145
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    AIChE Journal 41 (1995), S. 2187-2197 
    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 numerical computation of the LDV results of Kliafas and Holt is reported for a turbulent gas-solid particle flow in a square-sectioned 90° bend. A Eulerian model with generalized Eulerian solid surface boundary conditions for the particulate-phase momentum exchanges with solid walls are included. The turbulent closure is effected by using the gas-phase RNG-based k-∊ turbulence model, and the particulate turbulence diffusivity is related to the turbulent viscosity of the gas phase. Comparisons are made with experimental data for the mean streamwise velocities of both phases, the streamwise turbulence intensity of the gas phase, and the particulate concentration distribution in the bend. The localized high particulate concentration near the outer curve of the bend that occurs at large Stokes number is accurately predicted. Empirical computational evidence is presented for a relaxation of the minimum particle number density required to allow the use of a continuum model.
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  • 146
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    AIChE Journal 41 (1995), S. 2198-2211 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In roll coating as in other coating processes the coating liquid often suffers changes in properties on the time of the coating flow, that is, from fractions of a second upward depending on the amount of recirculation and recycling. The agents of change may be chemical reaction, colloidal aggregation, or evaporation. Hence the mean residence time and the residence time distribution of the liquid are important to designers and operators of coating processes. Here, building on the examination of roll-coating systems by Benjamin et al. (1995), the residence times of liquid coated by representative arrays of multiple rolls in the “forward roll” mode and relatively starved feed condition (neglecting the possibly significant effects of “rolling banks” and other internal recirculations when they are present) are analyzed. The dynamic response of these transfer coaters to step changes in the feed gap and to periodic gap changes, as from roll and bearing run-out, are also analyzed. No reports of operating or laboratory experiments are available for comparison. Nevertheless the results make plain how these quality-limiting features may depend don the number of rolls used; their sizes, speed, and arrangement, and the properties of the coating liquid.
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  • 147
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    AIChE Journal 41 (1995), S. 2250-2260 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Distributed parameter models of the single channel of a monolith combustor have been derived from progressively simplified assumptions. Simulation results are compared to assess the importance of the different physicochemical phenomena occurring in the combustor and to identify the simplest adequate model. For typical operating conditions of the hybrid combustor (gas and wall temperature not exceeding 1,073 and 1,273 K, respectively, high flow rate and pressure, natural gas as fuel), the results show that variations of gas properties have to be considered while homogeneous combustion can be neglected. Assumption of the approximate radial profile of axial velocity with invariant parabolic shape, rather than the rigorous solution of momentum balance and the continuity equation, provides accurate results. Moreover, for simulation of ceramic monoliths, backward heat transmission by wall conduction can be neglected with a substantial saving of computational labor.
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  • 148
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    AIChE Journal 41 (1995), S. 2274-2281 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In this work the experimental observations are explained with the aid of a simple air-entrapment model based on the concept of two levels of porosity of fiber mats. A simple model that includes liquid bypassing with initial air trapping, subsequent capillary invasion of regular fiber bundles with air compression, and finally mobilization is proposed to explain air-entrapment phenomena. The simple model successfully rationalizes the observed air trapping and compression during initial liquid-fiber contact. An empirical equation for the mobilization efficiency is adapted to the model to estimate void content. The velocity dependence of the trapped void content predicted by the model is in good agreement with observations.
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  • 149
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    AIChE Journal 41 (1995), S. 2282-2291 
    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 low-temperature nitridation of gallium arsenide, silicon and transition metals was investigated using hydrazine. Gallium nitride films were grown on gallium arsenide (GaAs) by direct reaction of the semiconductor surface layers with hydrazine et 200-400°C. Auger electron spectroscopy and X-ray photoelectron spectroscopy (XPS) analyses show that the films are primarily gallium nitride with a small oxide impurity. Thin nitride films (∼15 Å) were grown on silicon by reaction with hydrazine at 300-500°C. Ellipsometry results suggest that the film growth goes through different phases following linear, parabolic and logarithmic functions with time. XPS analysis shows that the nitride films could be formed at much lower temperatures than possible with ammonia (300 vs. 600°C). The formation of numerous transition metal nitrides (Co, Cr, Fe, Mo, Si, Ta, Ti, V, and W) by reaction with hydrazine at 400°C is demonstrated, as well as the chemical vapor deposition of boron nitride films from diborane and hydrazine reactants. The temperature at the mixing point was critical in determining the final composition of the film. A 1-D transport model suggests that the reaction rate at 400°C was kinetically limited. The results also agree qualitatively with thermodynamic equilibrium calculations.
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  • 150
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    AIChE Journal 41 (1995), S. 2314-2317 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 4 Ill.
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  • 151
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    AIChE Journal 41 (1995), S. 1281-1294 
    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 steady formation of fibers in the air-gap wet-spinning process is analyzed, in which solidification of the fiber material is brought about by the diffusional exchange of solvent and nonsolvent in a coagulation bath. The concentration profile within the fiber is determined, and a simple model is given for the change of the material behavior with changing concentration. The material behavior of the uncoagulated spinning solution is described by a constitutive model for viscoelastic liquids that allows the incorporation of a relaxation-time spectrum. The behavior of the solidified fiber is described by a model for rubberlike elastic solids. The effects of variable fiber temperature and skin friction on the fiber motion are also taken into account. The computed velocity profiles are compared to experimental data. These data were obtained by spinning three samples of nominally identical spinning solutions. Even though the theoretically predicted profiles agree well with those obtained with the first two samples, they completely fail to do so for the third. This failure is attributed to the unexpected extreme sensitivity of the model predictions to the width of the dynamic spectrum that is used to infer the relaxation-time spectrum. It is also found that the velocity profile depends rather strongly on the initial conditions for the stress.
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  • 152
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    AIChE Journal 41 (1995), S. 1306-1318 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Laser flash photolysis of the hydrogen abstraction reaction of triplet benzophenone (3BP) from 2-propanol and 1,4-cyclohexadiene in supercritical ethane and fluoroform was investigate. Bimolecular rate constants based on bulk concentrations decrease with an increase in pressure along both isotherms studied. These results corroborate our previous studies in CO2 that show increased reaction rates due to enhanced local compositions of cosolvent around the 3BP solute. Analysis of the results includes prediction of the thermodynamic pressure effect on the rate constant, which suggests an increase in the rate constant with pressure, as well as the effects of increased local cosolvent concentrations about 3BP. Spectroscopic measurements of the local composition of 2-propanol about a solute in supercritical CO2 are used to explain the apparent discrepancy between experiment and prediction, providing reasonable evidence that the local environment can influence kinetically controlled reactions in supercritical fluids.
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    AIChE Journal 41 (1995), S. 1324-1328 
    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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  • 154
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    AIChE Journal 41 (1995), S. 1337-1340 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 6 Ill.
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  • 155
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    AIChE Journal 41 (1995), S. 1346-1348 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 2 Ill.
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  • 156
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  • 157
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    AIChE Journal 41 (1995), S. 1357-1367 
    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 spreading of Newtonian liquid drops after impact with a solid surface is reproted for a range of liquid and surface proeprties, drop diameters, and impact velocities. Results for liquid viscosities up to 300 mPa.s are given. For a given drop diameter and velocity, a range of liquid viscosities result in splashing even for smooth surfaces. The maximum spread radius, made dimensionless with the drop radius, is correlated as Rmax* = 0.61(Re2Oh)0.166, where Re and Oh are the Reynolds and Ohnesorge numbers. respectively. A model is proposed to account for inertial, viscous, and surface tension forces on the maximum spread radius. Good agreement is found between the model and experimental data from several sources.
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  • 158
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    AIChE Journal 41 (1995), S. 1375-1388 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Earlier work of Sinclair and Jackson that treats the laminar flow of gas-solid suspensions is extended to model dilute turbulent flow. The random particle motion, often exceeding the turbulent flucutations in the gas, is obtained using a model based on the kinetic theory of granular materials. A two-equation low Reynolds number turbulence model is modified to account for the presence of the dilute particle phase. Comparisons of the model predictions with available experimental data for the mean and fluctuating velocity profiles for both phases indicate that the resulting theory captures many of the flow features observed in the pneumatic transport of large particles. THe model predictions did not manifest an exterme sensitivity to the degree of inelasticity in the particle-particle collisions for the range of solid loading ratios investigated.
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    AIChE Journal 41 (1995), S. 2427-2438 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Guildlines for the design of fractional crystallization processes to separate two-and three-solute mixtures are presented. By using solvent addition/removal, stream combination, and cooling/heating, these processes bypass regions of multiple saturation in the phase diagram and recover purse solutes. Design equations are formulated, and the constraints on the design variables are identified. also included is a discussion of the effect on recyle flows of changes in the design variables and an estimate of the cost of a fractional crystallization separation.
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    AIChE Journal 41 (1995), S. 201-202 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 161
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    AIChE Journal 41 (1995), S. 202-203 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 162
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    AIChE Journal 41 (1995) 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 163
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    AIChE Journal 41 (1995), S. 223-228 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Optical probes are used to study gas-solid fluidized-bed hydrodynamics. The probes each consisting of a light source and photodetector separated by a gap are suitable for use at combustion-level temperatures. The methodology to process the signal for calculation of bubble properties such as bubble frequency, local bubble residence time, bubble velocity, pierced length, bubble size, and visible bubble flow is presented. The signal processing technique is independent of bed operating conditions. The probe signal processing methodology is validated by comparing calculated bubble properties based on the probe signal with properties observed on videotapes of a 2-D bed.
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  • 164
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    AIChE Journal 41 (1995), S. 2508-2511 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 4 Ill.
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  • 165
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    AIChE Journal 41 (1995), S. 2499-2507 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Electrochromatography is a form of gradient liquid chromatography in which an axial electric potential is applied to columns packed with gel-filtration media. Experimental methodology and a mechanistic model are further developed for a system that minimizes Joule heating at electric field strengths of 100 V/cm by dissipating heat through a cooling jacket and use of a cooled, low ionic strength eluting buffer. Focusing of proteins can be achieved in a 15-mm-dia. Column by the interplay of eluent velocity, electrophoretic migration rate, and electrically induced concentration polarization when the stationary phase is more conductive than the mobile phase. Voltage gradients of up to 125 V/cm for eluent velocities at 18-25 cm/h separate binary protein mixtures of Bhb-α-lactalbumin, BSA-myoglobin, and α-lactalbumin-myoglobin over Sephadex G-100 and G-50. Retention times are consistent with values obtained from a mechanistic nonlinear model.
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    AIChE Journal 41 (1995), S. 58-67 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Theoretical models of gas diffusion and permeation in microporous molecularsieve membranes are presented. The effect of the adsorbed diffusant on the total transmembrane flow is insignificant for permanent gases. For highly adsorbable gases the effect of the adsorbed molecules on the total transmembrane flux may be high at low temperatures. The activation energy of diffusion increases when the kinetic diameter of the diffusant increases. The activation energy of gas diffusion compares well with the values calculated based on the Lennard-Jones potential. Maximum possible permeability coefficients calculated for He in the molecular-sieve membranes do not exceed ˜30,000 Barrer at room temperature. The experimentally observed value for He permeability is ˜1,000 Barrer (T=30°C) because of the high tortuosity (τ≍ 25) and low porosity (θ = 0.22) of the membrane porous structure.
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  • 167
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    AIChE Journal 41 (1995), S. 68-77 
    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 pH-stat MSMPR crystallizer is used to obtain the nucleation rate equation of calcite formed in the Na2CO3-CaCl2 reacting system. The experiments are conducted for seeded and unseeded runs. Effects of breakage and agglomeration on the crystalsize distribution are demonstrated. In a continuous operation, the agglomeration of nuclei followed by the breakage of agglomerates occurs at the transient state, while the agglomeration is significant at the steady state. Taking crystal agglomeration into account, the corrected nucleation rate and agglomeration rate are obtained simultaneously. The agglomeration rate is a function of relative supersaturation and magma density, and the corrected nucleation rate is approximately two- to five-fold of the apparent nucleation rate, which is the nucleation rate without considering the agglomeration effect. Discussed also is the formation of calcium carbonate polymorphism.
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  • 168
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    AIChE Journal 41 (1995), S. 78-96 
    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 separation system representation uses stream separation vectors in the separation space. The characteristics of a separation sequence are clarified by its separation base vectors that form the sequence basis and those of a separation system by the geometrical properties of separation vectors. The optimal flowsheet of each sequence under separation vector formulation can be obtained as the solution of a linearly-constrained optimization problem. A set of simple rules determines the minimum separation loads of any sharp separation sequence by inspection. A modified cost measure, which combines the separation cost with the savings due to stream bypass, can be used to select the optimal sequence without the overall cost analysis.The optimal separation sequence is obtained first by identifying the best sequence configuration according to modified cost measures and then by finding the actual costs of maximum-bypass and its neighboring sequence configurations. For the nonlinear objective function, the exact optimal flowsheet is determined by solving a linearly-constrained optimization problem. Since this procedure is a linearly-constrained optimization problem, the mathematical programming solution is not likely to lead to a local minimum.
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    AIChE Journal 41 (1995), S. 97-109 
    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 prototype hazard identification system, qualitative hazard identifier (QHI), works by exhaustively positing possible faults, automatically building qualitative process models, simulating them, and checking for hazards. QHI matches a library of general faults such as leaks, broken filters, blocked pipes, and controller failures against the physical description of the plant to determine all specific instances of faults that can occur in the plant. Faults may perturb variables in the original design model or may require building a new model. Fault models are automatically generated using the qualitative process compiler and simulated using QSIM. Hazards including overpressure, overtemperature, controller saturation, and explosion are identified in the reactor section of a nitric acid plant using QHI.
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    AIChE Journal 41 (1995), S. 691-700 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Transport of small molecules in heterogeneous materials can be an important factor in many engineering and biological applications. This study focuses on the diffusion of cellular nutrients in an immobilized cell system. A Monte Carlo simulation technique is used to describe the diffusion of small molecules in a variety of simulated cellular structures. Diffusivity predictions are in close agreement with experimental values as well as with theoretical bounds reported in the literature. It is revealed that effective diffusivities are highly dependent on the diffusivities of the species in the various phases and on the volume fraction of cells. The spatial arrangement of the cells, however, has no apparent effect on the predicted diffusivity for the range of conditions investigated.
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  • 171
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    AIChE Journal 41 (1995), S. 701-711 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Theories and experimental measurements related to the diffusion of globular macromolecules and small spheres in polymer solutions are discussed. It is shown that the Kirkwood-Riseman point scatterer and Brinkman models, two theoretical approaches that lead to hydrodynamic screening, are equivalent. Holographic interferometry is presented as a new method for measuring gradient diffusion of proteins in transparent polymer solutions and gels. This method is used to examine the effect of ionic strength, polymer concentration and polymer molecular weight on the diffusion of bovine serum albumin (BSA) in dextran solutions. The data are interpreted in light of the hydrodynamic screening and Stokes-Einstein models of diffusion. In particular, it is shown that while the Stokes-Einstein equation may be appropriate for the diffusion of relatively large latex spheres in polymer solutions, it is inappropriate for predicting diffusion coefficients of BSA and comparable proteins in such solutions.
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  • 172
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    AIChE Journal 41 (1995), S. 723-727 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 4 Ill.
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  • 173
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    AIChE Journal 41 (1995), S. 712-722 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Calcium magnesium acetate (CMA) is an effective dual SO2-NOx emission control agent. Laboratory-scale experiments with dry injected particles at a Ca/S molar ratio of 2 [or (Ca + Mg)/S ratio of 6] resulted in SO2 and NOx removal efficiencies of over 90% at gas temperatures of 950 - 1,250°C in atmospheres containing 12% CO2, 3% oxygen, 2,000 ppm SO2, and 1,000 ppm NOx during a 1-s residence time in an isothermal cavity followed by injection of after-fire air. During the experiments, SO2 reacted with the porous, thin-walled CaO, CaCO3 and MgO cenospheres, formed when CMA calcined, while NOx was reduced by hydrocarbon radicals from the organic acetate decomposition. While Ca was the dominant contributor to SO2 reduction by CMA in the isothermal furnace zone, Mg also contributed to SO2 reduction. At gas temperatures ≤ 950°C, Mg reacted directly with SO2 in the isothermal furnace zone and was the dominant SO2 remover in the post-furnace quenching zone while indirectly SO2 at higher isothermal zone temperatures by precluding pore-mouth plugging when CaSO4 formed. Interactions among hydrocarbons, SO2, and NOx are important but not fully understood.
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    AIChE Journal 41 (1995), S. 728-731 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 3 Ill.
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    AIChE Journal 41 (1995), S. 732-736 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 2 Ill.
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  • 176
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    AIChE Journal 41 (1995), S. 737-740 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 177
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    AIChE Journal 41 (1995), S. 741-741 
    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 41 (1995), S. 741-742 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
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    AIChE Journal 41 (1995), S. 742-743 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 41 (1995), S. 743-745 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
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    AIChE Journal 41 (1995), S. 745-746 
    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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  • 182
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    AIChE Journal 41 (1995) 
    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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  • 183
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    AIChE Journal 41 (1995), S. 749-763 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Use of saturation-dependent relative mobilities leads to linear flow; however, experiment and theory show that, in the limit of very large viscosity ratio, the flow is not linear but fractal. Generally, fractional flows and relative mobilities depend on both saturation and time. Use of a standard pore-level model of 2-D flow in the limit of infinite capillary number shows that this flow is fractal for large viscosity ratios (M = 10,000) and the sauration and fractional flows agree with the results of our general arguments. For realistic viscosities (M = 3 → 300), our modeling of the unstable flow shows that, although the flows are initially fractal, they become linear on a time scale, τ increasing as τ = τ0M0.17. Once linear, the saturation front advances as x ≈ v0M0.068 t; the factor M0.068 acts as a 2-D Koval factor.
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    AIChE Journal 41 (1995), S. 435-438 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 5 Ill.
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  • 185
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    AIChE Journal 41 (1995), S. 1229-1234 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Several methods have been proposed to improve the conversion of catalytic oxidation reactions. Gases with low enthalpy contents or gases that contain small amounts of combustible compounds can be converted much more efficiently in a reactor with reciprocating flow. The solid phase exhibits an inertia behavior insofar as it does not reach equilibrium with the gas temperature at the reactor ends. The solid-phase temperature at the center of the bed is considerably higher than in the unidirectional case. Results for the oxidation of CO at different inlet gas temperatures and switching periods are presented. An optimum period is found at which maximum conversion occurs. An estimate of the maximum temperature in the reactor is derived.
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  • 186
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    AIChE Journal 41 (1995), S. 1251-1265 
    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 comprehensive kinetic model developed for molecular weight calculations of ethylene axsnd α-olefin copolymerizations in the context of a terminal model accounts for multiple-type active centers of the catalyst, detailed elementary chemical reactions, and catalyst composition. The moments of copolymer chain distributions are defined considering molecular weights of comonomer units so that copolymer molecular weight averages can be directly calculated from those moments. A double Z-transformation is introduced for the derivation of differential equations of the moments. Model simulations are carried out based on ethylene and 1-butene copolymerizations in a gas-phase fluidized-bed reactor. Polydisperity of accumulated copolymer depends on catalyst composition and kinetic characteristics of the catalyst. For a catalyst with specified kinetic characteristics, the polydispersity depends on the mole fraction of each type of active center. For a catalyst with two types of active centers, the maximum polydispersity of copolymer occurs at 50 wt. % of the total copolymer if polydispersities of the copolymers generated at each active site are the same. Polydispersity of accumulated copolymer is sensitive to propagation reactions and chain transfer to hydrogen reactions. Differences in chain transfer to cocatalyst and monomers and in spontaneous deactivation rates for different types of active centers may play minor roles in controlling molecular weight development in the presence of hydrogen. This model can be used for catalyst composition design, simulation of commercial olefin copolymerization processes, and kinetic parameter estimation.
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  • 187
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    AIChE Journal 41 (1995), S. 1295-1305 
    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 ternary microemulsion systems alkane/water/DDAB (didodecyldimethylammonium bromide) form ideal model-disordered media. The static microstructure is described by a simple parameter-free model that can be predetermined and agrees with SAXS and SANS scattering experiments. The component volume fraction can be varied to exhibit bicontinuous random structures with a predicted percolation transition to disconnected water-in-oil droplets. Structural transitions are analyzed in the context of theories of percolative phenomena. Experimental transport properties agree well with model predictions based on an effective medium approximation. Critical exponents that describe the scaling of the transport properties near percolation are consistent with theoretical expectations near a static percolation transition. Through variation of component volume fractions a medium of known microstructure can be prescribed, so that independent measurement of transport and mechanical properties is possible.
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  • 188
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    AIChE Journal 41 (1995), S. 880-893 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: To predict the effect of pore structure on the performance of heterogeneous catalysts, a realistic model of the catalyst particle is required. Lattice-based models in which the diffusion and reaction phenomena are restricted to sites and bonds within a regular or irregular lattice are widely used. However, for the realistic simulation of diffusion and reaction in amorphous catalyst supports, such as alumina or silica, a continuum model, which does not artificially restrict the domain in which the reactants are allowed to diffuse, is required.An efficient method based on a “first passage time” approach is developed for the simulation of diffusion and reaction in a supported catalyst. The model catalyst is composed of spheres representing the support and active sites. By varying the algorithm used to generate the model catalyst, a range of structures can be created. The effect of the structure, and the size and distribution of active sites on the reaction rate is studied.
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  • 189
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    AIChE Journal 41 (1995), S. 868-879 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Fluidized-bed polyethylene reactors are prone to unstable behavior and temperature oscillations (Choi and Ray, 1985b). Their work is extended to show the effects of ethylene feed system operation, reactor cooling system design, catalyst properties, and gas composition on reactor stability and dynamics. The analysis is performed using a well-mixed model, because heat- and mass-transfer resistances between multiple phases are small and are not required to account for the observed bifurcation phenomena. The addition of a gas recycle and heat exchanger system to the model significantly affects dynamic performance, including the formation of limit cycles. The size and dynamics of the heat exchanger, however, have little effect on the overall stability. In contrast, automation of the ethylene feed system to replace the monomer in the reactor as it is consumed leads to substantially different dynamic behavior than if the ethylene feed is maintained at a constant rate. Catalyst properties (multiple sites, activation energy, and deactivation) significantly affect dynamics and stability, whereas comonomer and other gases affect them only mildly. The results confirm that without proper temperature control, gas-phase polyethylene reactors are prone to instability, limit cycles, and excursions towards unacceptable high-temperature steady states.
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  • 190
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    AIChE Journal 41 (1995), S. 907-914 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Microporous solids made by polymerizing the organic phase of bicontinuous microemulsions stabilized with didodecyldimethylammonium bromide show surface areas as high as 70 m2/g. Small-angle X-ray scattering measurements on microporous copolymers containing polymethylmethacrylate show that these areas result from structures larger than 250 Å that are generated during polymerization. These X-rays measurements also show that the 17-Å structures characteristics of the original microemulsion are retained during polymerization, but destroyed when the detergent is extracted and the solid is dried.
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    AIChE Journal 41 (1995), S. 915-923 
    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 dynamic interfacial tensiometer described measures the tension of stressed liquid-liquid interfaces. In this accurate and controlled method, the time-dependent pressure difference across the curved interface of a spherical drop, immersed in a second immiscible phase, is measured as a function of time. Dynamic experiments are conducted by varying the drop size, therby stressing the interface. The technique is eminently suited for the measurement of static and dynamic interfacial tensions, the study of the diffusion, adsorption, and desorption kinetics of surfactants, and the rheological behavior of liquid films. These capabilities are demonstrated for n-dodecane contacted with an aqueous solution of a nonionic surfactant. To explain the phenomena, diffusion models are developed that compare well with the experimental data. The noninvasiveness and versatility make this instrument a useful tool.
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    AIChE Journal 41 (1995), S. 938-947 
    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 method-based on evaporation of a constant-composition droplet containing two components that differ markedly in volatility accurately estimates activity coefficients of both components. This new technique is developed to simultaneously determine the evaporation rate and composition of a droplet from intensity peaks observed in the light scattered by the droplet. It has no upper or lower limits on the relative volatility of the system and is particularly suitable for systems containing one relatively nonvolatile component. The data on the glycerol-ethanol system, obtained from evaporation of glycerol droplets in ethanol vapor and correlated with Margules and Wilson equations, are thermodynamically consistent. The results of this study agree with ethanol activity coefficients calculated from the total pressure vs. solution composition data previously reported.
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    AIChE Journal 41 (1995), S. 948-948 
    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 41 (1995), S. 949-953 
    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 41 (1995), S. 991-995 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 4 Ill.
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    AIChE Journal 41 (1995), S. 974-984 
    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 theoretical model for investigating physical phenomena underlying immune complex formation was developed, based on the statistical mechanical theory of associating fluids that identifies each molecule as a hard sphere with a nested point charge and vector dipole. The interaction between binding molecules (epitope-paratope binding) is represented as a cone truncated by two concentric spheres in which the potential energy is a modified square well with respect to particle separation and a square well with respect to mutual molecular orientation. Equilibrium binding results predicted by the model show good agreement with results obtained experimentally for a model system containing a single antigen and a single monoclonal antibody [bovine serum albumin (BSA) - anti-BSA antibody]. Moreover, values obtained for the system isothermal compressibility and the second virial coefficient by both the model and light scattering experiments also show good agreement with one another.
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    AIChE Journal 41 (1995), S. 1010-1014 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 2 Ill.
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    AIChE Journal 41 (1995), S. 1015-1024 
    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 formation of aggregates, rather than correctly folded polypeptide chains, is a pressing problem in biotechnology that has been difficult to approach quantitatively. The competition between folding and aggregation has been carefully analyzed for bovine growth hormone (bGH) and can be attributed to incorrect helix-helix docking for this four-helix bundle protein. An extended molecular thermodynamic model reported here represents Gibbs energy changes associated with intramolecular and intermolecular helix-helix dockings occurring during protein folding and protein aggregation. The model incorporates (1) a semiempirical local composition Gibbs energy expression to account for the helix-helix hydrophobic interactions, which favor helix-helix docking and aggregation and (2) a Flory-Huggins-type Gibbs energy expression to describe the configurational entropy of the polypeptide backbone conformation, which favors disaggregation. For the folding and aggregation of bGH, the molecular thermodynamic model provides estimates for the Gibbs energies and thermodynamic stabilities of various conformations of bGH and qualitatively accounts for the competition between aggregation and productive folding. It also successfully describes the inhibition of aggregation found with peptides corresponding to bGH helical sequences and the effect of site-directed mutagenesis.
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    AIChE Journal 41 (1995), S. 1037-1040 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Additional Material: 6 Ill.
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    AIChE Journal 41 (1995), S. 1044-1044 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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