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  • 1
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 32 (1986), S. 1253-1262 
    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 universally valid formal expression for the composition dependence of solute and solvent fugacity coefficients in any dilute binary system far from criticality is derived in this paper. In the present context, dilution denotes the y1 → O limit, regardless of the mixture's molar density. The results are independent of the system under study and of the choice of equation of state. The solute fugacity coefficient is simply the product of a composition-independent term (the infinite dilution fugacity coefficient) and an exponential decay composition correction. These two parameters have important thermodynamic implications: their temperature and pressure derivatives are related to the solute's partial molar enthalpy and volume, respectively. When applied to activity coefficients, the same theoretical analysis yields universal relationships for the composition dependence of activity coefficients which can be used as consistency checks for empirical correlations. The relationship between infinite dilution activity and fugacity coefficients can be used to estimate relative solubilities of a given solute in different solvents. Excellent agreement is found when the theoretical expressions are tested with three different binary systems involving a nonvolatile solid solute and a supercritical fluid.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 32 (1986), S. 2034-2046 
    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 different behavior of fluid density and viscosity in going from the dilute gas to the dense fluid state gives rise to kinematic viscosities which, in the near supercritical region, are lower than for liquid metals. As a consequence, the relative importance of natural convection (as measured by the ratio of buyoant to inertial forces) is two orders of magnitude higher in a supercritical fluid (at constant Reynolds number) than in normal liquids.Binary diffusion coefficients of nonvolatile solutes in supercritical fluids were measured with a technique that involved laminar flow and diffusion in a rectangular channel. The solution to this hydrodynamic problem is presented. By varying the inclination of the solute source plane with respect to the horizontal position, apparent diffusion coefficients were measured that were up to six times higher than the “true” coefficients.Experimental binary diffusion coefficients, including published literature data, were analyzed in the light of hydrodynamic (Stokes-Einstein) theory. The analysis suggests that under the high-density, low-viscosity conditions that characterize supercritical fluids, hydrodynamic behavior at the molecular level is approached, and can be used as a basis for data extrapolation.
    Additional Material: 15 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 33 (1987), S. 1406-1407 
    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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  • 4
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 34 (1988), S. 645-657 
    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 behavior of solute partial molar enthalpies in dilute supercritical mixtures gives rise to the well-known phenomenon of retrograde solubility (equilibrium solubility decreasing with increasing temperature at constant pressure). A mechanistic interpretation of this phenomenon in terms of the formation of large clusters of solvent molecules around solute molecules is consistent with experimentally observed retrograde behavior. Cluster formation occurs as a consequence of the unbounded increase in the solvent's compressibility arbitrarily close to the latter's critical point. At infinite dilution, the solute's partial molar volume and enthalpy grow linearly with cluster size. This means that the negative divergence of these quantities is simply a macroscopic manifestation of a “condensation” in which an increasing number of solvent molecules cluster around solute molecules. Arbitrarily close to the solvent's critical point, scaling relationships show that the decay of both solvent-solvent and solute-solvent correlation functions exhibits the same radial dependence. This functionality is thus solute-independent, and is determined exclusively by the proximity to the solvent's critical point. The locus along which thermal effects associated with cluster formation are maximized is arbitrarliy close to the solvent's critical isochore as the latter's critical point is approached.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 34 (1988), S. 447-455 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: If a given liquid exhibits a density maximum anywhere in its phase diagram, thermodynamic consistency dictates that such a point cannot be isolated: a density maxima locus must necessarily exist. For a fluid that does not also exhibit density minima, the pressure-temperature projection of such a locus is negatively sloped, and can only end at a stability limit. There exist two thermodynamically consistent ways in which such an intersection can occur, and they correspond, respectively, to the highest and lowest possible temperatures at which a liquid can exhibit a negative coefficient of thermal expansion. These theoretical predictions are confirmed by experimental observations. The existence of density anomalies anywhere in a liquid's phase diagram is shown to have a profound influence in determining the shape of such a fluid's stability boundary.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 34 (1988), S. 1211-1214 
    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: 1 Ill.
    Type of Medium: Electronic Resource
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  • 7
    ISSN: 1862-0760
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract Coal gasification in molten metal baths is a relatively new process with important technological advantages. The economics of the process can be made even more attractive if part of the Gibbs energy change of the oxidation reaction is directly converted into electricity through the use of the concept of a solid oxide fuel cell. This combination of fuel cell and fused metal gasifier in a single reactor-cell of the type: C, O2, fused metal / YSZ / perovskite, O2 is the distinguishing feature of the new process analyzed in this work. A mathematical model has been developed which describes the steady-state behaviour of this novel fuel cell and discusses the effect of operating conditions upon cell performance. This theoretical approach shows that, under best-case estimates, the electrochemical cell gasifier is capable of producing very high current and power densities.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 3001-3005 
    ISSN: 0887-6266
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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