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A new expression is presented for estimating the dielectric constant of a fluid mixture as a function of temperature, density and composition. The estimated dielectric constants (and their derivatives) are required for phase-equilibrium calculations, based on an equation of state, for systems containing electrolytes and nonelectrolytes. The new expression holds for the entire range of fluid densities, from zero to liquid-like densities. Mixing of components is performed on a volume-fraction basis at constant temperature and constant reduced density. For polar components where data are not available at the temperature and/or reduced density of interest, the well-characterized behavior of water is used to extrapolate the available pure-component data. The importance of using the correct density of the mixture is shown. Using one adjustable parameter for each nonideal binary subsystem, predicted results can be significantly improved. 相似文献
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Paul H. Prausnitz 《Colloid and polymer science》1930,50(1):77-85
Ohne Zusammenfassung
Vortrag gehalten am 7. Juni 1929 vor der Medizinisch — Naturwissenschaftlichen Gesellschaft in Jena und dem Bezirksverein
Thüringen des Vereins Deutscher Chemiker. 相似文献
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Solubilities of several solvents were measured in four molten polymers by using an isobaric vapor-pressure apparatus. Solvent concentration ranged from 0.5 to 15 wt-%. The systems polyisoprene–benzene and polyisobutylene–benzene were studied at 80.0°C; polyisobutylene–cyclohexane was studied at 100.0°C; ethylene–vinyl acetate copolymer (EVA)–cyclohexane, EVA–isooctane, and poly(vinyl acetate)–isooctane were studied at 110.0°C. Of six polymer–solvent systems studied, all except poly(vinyl acetate)–isooctane appear to exhibit hysteresis in a single sorption–desorption cycle starting with dry polymer. The desorption curves of solvent activity plotted versus solvent weight fraction show an inflection point, suggesting localized adsorption of solvent molecules. Experimental data were analyzed with a theory which takes into account adsorption of solvent by polymer in addition to differences in free volumes and intermolecular forces. The theory gives a semiquantitative representation of the experimental data. 相似文献
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Boström M Tavares FW Ninham BW Prausnitz JM 《The journal of physical chemistry. B》2006,110(48):24757-24760
Monte Carlo simulations are used to establish the potential of mean force between two globular proteins in an aqueous electrolyte solution. This potential includes nonelectrostatic contributions arising from dispersion forces first, between the globular proteins, and second, between ions in solution and between each ion and the globular protein. These latter contributions are missing from standard models. The potential of mean force, obtained from simulation, is fitted to an analytic equation. Using our analytic potential of mean force and Barker-Henderson perturbation theory, we obtain phase diagrams for lysozyme solutions that include stable and metastable fluid-fluid and solid-fluid phases when the electrolyte is 0.2 M NaSCN or NaI or NaCl. The nature of the electrolyte has a significant effect on the phase diagram. 相似文献
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Y. U. Moon R. A. Curtis C. O. Anderson H. W. Blanch J. M. Prausnitz 《Journal of solution chemistry》2000,29(8):699-718
Osmotic pressures have been measured to determine lysozyme—lysozyme,BSA—BSA, and lysosyme—BSA interactions for protein concentrations to 100 g-L–1in an aqueous solution of ammonium sulfate at ambient temperature, as a functionof ionic strength and pH. Osmotic second virial coefficients for lysozyme, forBSA, and for a mixture of BSA and lysozyme were calculated from theosmotic-pressure data for protein concentrations to 40 g-L–1. The osmotic second virialcoefficient of lysozyme is slightly negative and becomes more negative withrising ionic strength and pH. The osmotic second virial coefficient for BSA isslightly positive, increasing with ionic strength and pH. The osmotic second virialcross coefficient of the mixture lies between the coefficients for lysozyme andBSA, indicating that the attractive forces for a lysozyme—BSA pair areintermediate between those for the lysozyme—lysozyme and BSA—BSA pairs. For proteinconcentrations less than 100 g-L–1, experimental osmotic-pressure data comparefavorably with results from an adhesive hard-sphere model, which has previouslybeen shown to fit osmotic compressibilities of lysozyme solutions. 相似文献
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Francesco Fornasiero Darren Tang Ali Boushehri John Prausnitz C.J. Radke 《Journal of membrane science》2008,320(1-2):423-430
A novel evaporative cell is used to measure steady-state gradient-driven diffusion rates of water through hydrogel membranes in the absence of external mass-transfer resistance. In this cell, the bottom surface of a hydrogel membrane is exposed to pure water vapor at known activity (aw) less than unity, while a sealed liquid-water reservoir bathes the upper membrane surface. Induced by the chemical-potential gradient between the two surfaces, the water evaporation rate is monitored by the rate of weight loss of the water reservoir.Results at ambient temperature are compared with those from measured water flux through soft-contact-lens (SCL) materials and with other published experimental results. Concentration-dependent water diffusivities are obtained by interpreting measured water fluxes for 0.11 ≤ aw ≤ 0.93 with extended Maxwell–Stefan (EMS) diffusion theory. Thermodynamic non-ideality is taken into account through Flory–Rehner polymer–solution theory. Shrinking/swelling is modeled by conservation of the total polymer mass assuming volume additivity. In spite of correction for thermodynamic non-ideality, EMS–water-diffusion coefficients increase with the water volume fraction, especially strongly for those hydrogel materials with low liquid-saturated water contents. The evaporation cell described here provides a simple robust method to establish water transport rates through soft-contact-lenses and other hydrogel membranes without the need to correct for external mass-transfer resistance. 相似文献