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  • Wiley-Blackwell  (166)
  • 1
    Electronic Resource
    Electronic Resource
    Molecular thermodynamics of solute-polymer-supercritical fluid systems (1991)
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 37 (1991), S. 607-616 
    Details
    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 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.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/aic.690370414
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  • 2
    Electronic Resource
    Electronic Resource
    Molecular thermodynamics of solubilities in gas antisolvent crystallization (1991)
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 37 (1991), S. 1441-1449 
    Details
    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 expanded liquid molecular thermodynamic model is developed to predict the solubilities of pure solids in a liquid expanded with a gaseous antisolvent. Experimental data are presented for systems containing naphthalene, phenanthrene, and a mixture of both in toluene expanded with a gas antisolvent, CO2. The pressure range is 1 to 64 bar and the temperature is 25°C. The data are predicted accurately with regular solution theory up to moderate pressures, but not at the higher pressures where the liquid phase is nearly pure CO2. In contrast, the new expanded liquid equation of state model describes the wide range of behavior from the nearly ideal liquid solution at ambient pressure to the highly nonideal compressible fluid at elevated pressures. As a result, it predicts solubilities accurately over three orders of magnitude by using only binary interaction parameters. The implications of the phase behavior on fractional crystallization with a gas antisolvent are discussed.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/aic.690371002
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  • 3
    Electronic Resource
    Electronic Resource
    Probability density estimation using elliptical basis functions (1994)
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 40 (1994), S. 1639-1649 
    Details
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Elliptical basis function (EBF) networks are introduced as a new nonparametric method of estimating probability density functions for process data. Unlike Parzen window density estimators that use identical hyperspherical basis functions, the EBF method uses elliptical basis functions adapted to the local character of the data. This technique overcomes the spikiness problem associated with Parzen windows, where in high dimension, they can fail to produce smooth probability density estimates. The EBF estimator produces valid density functions that converage to the underlying distribution of the data in the limit of an infinite number of training examples. A technique based on statistical cross validation is introduced for evaluating different density estimators. The criterion is a measure of how well the density estimator estimates the density of data not used in the training. The EBF density estimation method and the evaluation technique are demonstrated using several examples of fault diagnosis.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/aic.690401006
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  • 4
    Electronic Resource
    Electronic Resource
    Behavior of countercurrent liquid-liquid columns with a liquid metal (1971)
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 17 (1971), S. 14-18 
    Details
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Packed columns are being considered for contacting liquid metals with molten salts to extract fission products from spent nuclear fuel. Extraction rates between a liquid cadmium alloy and a liquid chloride salt were measured at 530°C. in a prototype column. With a system of water and a low melting metal alloy, measurements of the pressure drop, limiting flow rates, and hold-up were made and compared with the predictions of existing correlations. These data indicate that packed columns might be effective contacting devices for pyrochemical processes.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/aic.690170107
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  • 5
    Electronic Resource
    Electronic Resource
    Extreme solvent effects on reaction rate constants at supercritical fluid conditions (1987)
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 33 (1987), S. 2017-2026 
    Details
    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 reaction rate constant was adjusted continuously over two orders of magnitude for the unimolecular decomposition of α-chlorobenzyl methyl ether using the supercritical fluid solvent 1, 1 diffluoroethane. Activation volumes were observed as low as -6,000 cm3/mol, which is about an order of magnitude more negative than those reported previously in the literature for a homogeneous reaction. Spectral shift (solvatochromic) data were measured for phenol blue in the same fluid in order to interpret the rate data. A method is presented to predict solvent effects on rate constants at supercritical fluid conditions.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/aic.690331212
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  • 6
    Electronic Resource
    Electronic Resource
    Partial derivative quantities from phase equilibria relationships for mixtures (1993)
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 39 (1993), S. 1363-1369 
    Details
    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 formulation of multicomponent/multiphase phase equilibria as a linear algebra problem in the fugacities, mole fractions, partial molar volumes, and partial molar enthalpies is given. The algorithm takes advantage of the Gibbs-Duhem relationships for each phase and a modified Gaussian elimination technique to reduce the system of equations. These algorithmic steps allow current symbolic manipulation packages to generate useful partial derivative relationships in terms of measurable thermodynamic quantities. Features of the algorithm are demonstrated by applying a computer implementation of the method to a simple two-phase/two-component system and to the more complicated examples of a two-phase/three-component supercritical fluid chromatography experiment and a mass-conserving closed system.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/aic.690390813
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  • 7
    Electronic Resource
    Electronic Resource
    Rate constants and molecular structure (1959)
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 5 (1959), S. 277-284 
    Details
    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 methods of relating parameters in the Arrhenius rate equation to fundamental molecular properties are briefly reviewed. The limited applicability of purely theoretical methods is noted, the use and limitations of the standard semiemprical method are surveyed, and recent work based on empirical molecular structure and spectroscopy is described in detail. The recent method makes no attempt to calculate activation energy, but within a limited range of cases it does provide a reliable method of estimating the preexponential factor in the Arrhenius equation and calculating the kinetic isotope effect. In this way the method provides a check on the credibility of experimental data and on the assignment of mechanism. If the mechanism is correct, it provides a method of estimating activation energy from rate data taken at only one temperature. Further developments of this method are anticipated.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/aic.690050306
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  • 8
    Electronic Resource
    Electronic Resource
    An analytical Carnahan-Starling-van der Waals model for solubility of hydrocarbon solids in supercritical fluids (1981)
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 27 (1981), S. 773-779 
    Details
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Data have been taken by a new flow technique for the solubility of nonpolar hydrocarbons in nonpolar supercritical fluids. These results for molecularly simple molecules provide a basis for the analytical representation of such systems by relatively simple equations of state.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/aic.690270511
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  • 9
    Electronic Resource
    Electronic Resource
    Adjustable solute distribution between polymers and supercritical fluids (1989)
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 35 (1989), S. 1097-1106 
    Details
    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 of toluene, dilute in CO2, and likewise the distribution coefficient of toluene between silicone rubber and CO2 have been explored from gaseous to supercritical fluid conditions. Sorption and desorption isotherms were determined by frontal analysis using a new inverse supercritical fluid chromatography technique at 35 and 70°C up to 250 bar. Complementary swelling data are presented for pure CO2 in silicone rubber up to 315 bar. A new result is that the sorption of toluene goes through a maximum and is highly adjustable over a continuum in the highly compressible region of carbon dioxide. This behavior is explained physically and predicted quantitatively with the Flory equation and the Peng-Robinson equation of state using only information from binary systems. These results are useful for a wide variety of applications including impregnation of polymers with pharmaceuticals, fragrances and other additives, and polymer purification.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/aic.690350705
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  • 10
    Electronic Resource
    Electronic Resource
    Letters to the editor (1990)
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 36 (1990), S. 1927-1930 
    Details
    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
    URL: http://dx.doi.org/10.1002/aic.690361221
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